TECHNICAL FIELD
[0001] The present document relates to the field of inkjet papers and methods for making
them, and it in particularly relates to inkjet papers with quick drying properties
and high-gloss.
BACKGROUND OF THE INVENTION
[0002] As outlined in
WO 01/45956, ink-jet printers will produce an image on most papers, but the print quality varies
heavily in dependence on the nature of the paper used. By "print quality" is meant
factors such as the sharpness, intensity and uniformity of the image produced and
its susceptibility to smudging immediately or shortly after the ink has been applied.
In the case of colour printing, it is important also that the colours should not run
into one another and that they should be vivid, with good brightness.
[0003] In order to achieve the highest quality colour images, with vivid bright colours
which do not run into one another, it is necessary to e.g. apply a pigment coating
to the paper. The pigment coating makes the paper highly absorptive to the aqueous
ink vehicle, so that the vehicle drains away quickly into the body of the paper, leaving
the coloured dye at the surface and thereby giving bright intense colours with minimal
print bleed.
[0004] A wide variety of pigments has been proposed for such coatings, and
WO 01/45956 states the use of gel-type silicas to be necessary to give the desired print quality.
However, such silicas are expensive, and because of their rheological characteristics,
they can only be used at relatively low solids content. This creates either a heavy
drying load or a reduced machine speed at limited drying capacity.
[0005] The most widely used general-purpose paper coating pigments are kaolin and calcium
carbonate, particularly precipitated calcium carbonate (PCC). They have been used
or proposed for use in coated ink jet papers, but primarily as extenders or in low-cost
papers not designed to produce the highest quality colour images.
[0006] In view of the above problems,
WO 01/45956 proposes to use a speciality cationic PCC product according to
WO-A-96/29369A which is much cheaper than silica pigments, and is easier to use from a rheological
standpoint in combination with a minor proportion of gel-type silica included in the
formulation, and all this for an image receiving top coating layer. Remaining disadvantage
is the relatively low solids content of the coating formulation.
[0007] US 598 5424 discloses a method comprising coating a base coat on a support, said base coat comprising
precipitated calcium carbonate and calcinated clay at a solids content of 60%.
WO2006/003391 discloses an inkjet receiver comprising a support; an upper layer comprising a binder
and a first inorganic particulate material having a mean particulate diameter of 500
nm or less, as well as an under layer comprising a binder and an inorganics particulate
material.
EP1114735 discloses an inkjet paper comprising a support and (i) a base coating comprising
75 parts of precipitated calcium carbonate and 25 parts of precipitated silica and
a binder and (ii) an ink-receptive top coating comprising fumed alumina.
SUMMARY OF THE INVENTION
[0008] The object of the present invention is therefore to provide an improved inkjet paper
eliminating at least one of the disadvantages mentioned above and/or providing an
economically and technically viable alternative to the solutions according to the
state-of-the-art.
[0009] The present invention solves the above problem by providing a method for making an
ink jet paper as detailed further below as well as an inkjet paper comprising two
layers, an image receiving coating layer for gloss and a pre-coat layer for printing
ink vehicle absorption beneath this image receiving coating layer, wherein these two
coating layers both have specific coating formulations and both having a clear positive
effect upon the printing properties. It is to be noted that the specific choice as
given below provides a solution to the difficult problem to provide a coating which
on the one hand can be of high-gloss and quick ink-drying, can be printed with most
commercial inkjet printers/colours leading to vivid colours without bleeding and similar
effects, and additionally a coating that can be run on a normal coating machine such
as a blade coater without problems. So the specific proposed choice of a specifically
designed image receiving coating layer with a further specifically designed pre-coating
layer has to be regarded not as a simple superposition of these two layers but as
a synergetic system in as far as adherence and ink receiving properties concerned
etc.
[0010] One of the key features of the invention is therefore the fact that the proposed
inkjet paper comprises at least one image receiving coating layer and at least one
pre-coat layer beneath said image receiving coating layer on a paper substrate, wherein
the pre-coat layer comprises a specific formulation as follows:
100 parts in dry weight of a pigment part consisting of
20-75 parts in dry weight of at least one type of fine particulate calcium carbonate
and/or kaolin;
5 - 70 parts in dry weight of at least one type of fine particulate silica and/or
of a fine particulate ground calcium carbonate with surface and internal structure
modification as a result of treatment with one or more medium to strong H3O+ ion providers and optionally with additional treatment of gaseous carbon dioxide;
and
0 - 30 parts of additional fine particulate pigments
4 - 20 parts in dry weight of a binder part
0-6 parts in dry weight of additives.
[0011] At the same time the image receiving coating layer also comprises a specific formulation
as follows:
100 parts in dry weight of a pigment part consisting of
50 - 100 parts in dry weight of at least one type of fine particulate silica; and
0 - 50 parts in dry weight of at least one type of fine particulate polymer, e.g.
plastic or biopolymer pigment; and
0 - 30 parts of additional fine particulate pigments
2 - 10 parts in dry weight of a binder
0-3 parts in dry weight of additives.
[0012] The total coating recipe of the pre-coat layer and/or of the image receiving coating
layer is chosen to be in an overall anionic state. This is in contrast to conventional
inkjet coating formulations, in which normally in at least one of the coating layers,
normally in the ink receptive coating layer, specifically a cationic total coating
system is provided to fix the anionic inkjet dyes. One such conventional inkjet coating
formulation based on a purely cationic topcoat layer is for example described in
EP 1114735, where for an ink receptive top coating fumed alumina particles with a cationic surface
charge are used in order to fix the anionic inkjet dyes, this effect is even supplemented
by adding a cationic fixative in a high amount. The cationic nature of the pigment
of the ink receptive top coating layer is important according to this document
EP 1114735 as if this pigment is partially replaced for example by colloidal silica, the colloidal
silica has to be a cationic and therefore very specific type of colloidal silica.
[0013] It is one of the surprising findings according to the present invention that it is
possible to use coating layers of anionic overall nature for an inkjet paper and still
to be able to fix the conventional inkjet dyes and to have the possibility of a glossy
surface appearance. The fixing of the conventional inkjet dyes in these anionic coating
layers can be supported by the presence of cationic systems like mordants which however
are added to the coating in an amount small enough such that the overall coating is
still anionic.
[0014] The additional fine particulate pigments can be selected from (preferably anionic)
pigments such as carbonate, in particular calcium carbonate such as precipitated or
ground calcium carbonate, clay, silica, in particular silica gel or colloidal silica,
kaolin, talc, as well as combinations and mixtures thereof.
[0015] One of the important constituents of the image receiving coating layer and/or of
the pre-coat layer is the fine particulate silica. In the pre-coat layer this can
either be replaced or supplemented by a specific porous carbonate pigment, more specifically
by a fine particulate ground calcium carbonate with surface and internal structure
modification as a result of treatment with one or more medium to strong H
3O
+ ion providers and optionally with additional treatment of gaseous carbon dioxide.
Specifically it was found that using the proposed fine particulate ground calcium
carbonate with (nano-sized) surface and internal (pore) structure modification, as
e.g. disclosed in
US 6,666,953 but without necessarily an involved treatment with gaseous carbon dioxide, and as
for example available from Omya, CH under the trade name Hydrocarb V70, preferably
of the type Hydrocarb V70 R240 ME, on the one hand provides for printing ink vehicle
absorption and fast to very fast ink setting properties even if not being the sole
constituent of the pigment part. It was specifically found that it is possible to
reach overall very fast ink setting properties similar to the ones which can be achieved
if fine particulate silica is present in the pigment part, so the proposed specific
pigment can be used to at least partially replace if not fully supplement or replace
fine particulate silica in the coating while however maintaining similar if not equivalent
overall very fast ink setting properties. This is a major achievement as a silica
gel is not only difficult to handle in the coating process (e.g. problem of low solids
of silica aqueous pigment slurries and prepared coatings and problem of dust formation)
and leads to a number of side-effects of the prepared coatings which have to be corrected
for e.g. by additional constituents of the coating formulation, but in addition to
that the replacement provides a very attractive cost advantage as silica gel pigments
usually are relatively expensive.
[0016] It should be noted that if the specific type of fine particulate ground calcium carbonate
with surface and internal structure modification is used, in the pre-coat formulation
the: content of may go down to a minimum of one part in dry weight even, the other
pigments complementing to 100 parts in dry weight.
[0017] A preferred embodiment of this aspect of the invention is characterised in that the
fine particulate ground calcium carbonate with surface and internal structure modification
and optionally an additional treatment with gaseous carbon dioxide has a median particle
size in the range of approximately 1.5-2.5 µm. It is also advantageous if the fine
particulate ground calcium carbonate with surface and internal structure modification
and optionally an additional treatment with gaseous carbon dioxide has an average
internal pore size in the range of 0.01-0.1 µm, preferably in the range of 0.03-0.08
µm, most preferably around 0.05 µm. Indeed this specific range of around 0.05 µm,
to provide high driving force for fast absorption rate and supplemented by a parallel
system of interconnected intra-particulate pores or voids in the total pigment matrix
with average pores or voids diameter of approximately 0.1 - 1 µm for effective overall
ink vehicles transport seems to be well matched to typical offset printing inks leading
to very advantageous printing properties. Specifically, a pore system including the
above Hydrocarb V70 and a corresponding matrix, optionally provided by a PCC pigment
as detailed below, appears to be well matched, and 50 nm driving force pores seem
to be similarly powerful as in case of silicagel with typical size range of 10-30
nm pores. Without being bound to any theory, it seems that the parallel traffic system
of relatively larges pores in case of pigments of the type of Hydrocarb V70 plus (or
combined with) a matrix, optionally based on such PCC, is even somewhat more effective.
[0018] Further the fine particulate ground calcium carbonate with surface and internal structure
modification and optionally an additional treatment with gaseous carbon dioxide preferably
has a surface area in the range of 30-80 m
2/g, preferably in the range of 50-70 m
2/g. Furthermore the fine particulate ground calcium carbonate with surface and internal
structure modification and optionally an additional treatment with gaseous carbon
dioxide can advantageously have a particle size distribution such that 73-83% of the
particles is smaller than 2 µm, and that 35-44% of the particles is smaller than 1
µm.
[0019] A very good porosity ideal for fast ink setting properties of the final high gloss
paper can be achieved if the fine particulate ground calcium carbonate with surface
and internal structure modification and optionally an additional treatment with gaseous
carbon dioxide is preferably of the so-called roses type. This means that the individual
particles of this pigment with a clustered nano-sized platelet structure and with
internal nano-sized pores are of generally round and almost spherical shape, and they
look similar to if not identical to the ones as disclosed in annex 4 of
US 2006/0162884. Also other Hydrocarb V70 forms are possible, e.g. the so-called eggs, golf balls,
brains and Beluga/Kaviar types as disclosed e.g. in the publications
Achieving Rapid Absorption and Extensive Liquid Uptake Capacity in Porous Structures
by Decoupling Capillarity and Permeability: Nanoporous Modified Calcium Carbonate,
in Transport in Porous Media vol. 63, nr. 2, pp. 239-259, May 2006; or
Achieving Rapid Absorption and Extensive Liquid Uptake Capacity in Porous Structures
by Decoupling Capillarity and Permeability: Nanoporous Modified Calcium Carbonate,
in Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 236, Issues
1-3, pp. 91-102, April 1, 2004.
[0020] According to a first preferred embodiment of the invention, the pre-coat layer uses
one or several standard fine particulate calcium carbonates, preferably a precipitated
(PCC) or ground (GCC) calcium carbonate type. Preferred is a standard anionic PCC
type with a surface area in the range of 2-40 m
2/g. The carbonates can be intrinsically porous types, for example the above-mentioned
fine particulate ground calcium carbonate type with surface and internal structure
modification.
[0021] According to a further preferred embodiment, the pre-coat layer comprises 100 parts
in dry weight of a pigment part consisting of 40-75 parts in dry weight, preferably
50-60 parts in dry weight, of a fine particulate ground or precipitated calcium carbonate;
25-70 parts in dry weight, preferably 40-60 parts in dry weight of at least one fine
particulate silica pigment and/or of a fine particulate ground calcium carbonate with
surface and internal structure modification as a result of treatment with one or more
medium to strong H
3O
+ ion providers and optionally with additional treatment of gaseous carbon dioxide.
[0022] For cost reasons but also for managing bleeding problems which might exist if the
silica part in the pre-coat consists of colloidal silica only, it can be advantageous
to combine within the silica part of colloidal silica and a silica gel. A certain
minimum amount of silica gel is necessary for achieving this reduced bleeding behaviour,
however for rheological reasons the silica gel contents should not be too high. Correspondingly
therefore it is advantageous if the fine particulate silica pigment in the pre-coat
layer is composed of 5-50, preferably 10-50 parts in dry weight of a colloidal silica
and 10-40 parts in dry weight of a silica gel. Even more beneficial effects can be
achieved if the fine particulate silica pigment in the pre-coat layer is composed
of 10-30, preferably 15-30, parts in dry weight of a colloidal silica and of 20-35,
preferably 25-35 parts in dry weight of a silica gel. The silica gel in the pre-coat
layer can have a particle size distribution such that the average particle size is
in the range of 0.1-10 µm, preferably below 7 µm and most preferably below 4.0 µm.
Preferably the pore volume of the silica gel is above 1.0 cm
3/g, more preferably more than 1.5cm
3/g. The colloidal silica in the pre-coat layer can have a particle size distribution
such that the average particle size is in the range of 10 - 120 nm, preferentially
40 - 100nm.
[0023] A further preferred embodiment of the present invention is characterised in that
the binder part in the pre-coat layer comprises a latex binder and a second binder
selected from the group of polyvinyl pyrrolidone binder, PVA, gelatine and mixtures
thereof. Specifically it is advantageous if the binder part comprises 2-20, preferably
2-14 (or even 2 - 6) parts in dry weight of a latex binder, preferably a styrene butadiene-binder
and 2-8, preferably 4-8 parts in dry weight of a polyvinyl pyrrolidone binder, preferably
of polyvinyl pyrrolidone with a molecular weight of more than 20'000 Da, even more
preferably of more than 30'000 Da, most preferably in the range of 40'000 Da - 80'000
Da.
[0024] A still further preferred embodiment of the present invention is characterised in
that the pre-coat layer comprises 100 parts in dry weight of a pigment part consisting
of 50-75 parts in dry weight, preferably 40-60 parts in dry weight, of a particulate
ground or precipitated calcium carbonate, wherein the particulate calcium carbonate
has a particle size distribution such that 60% of the particles are smaller than 2
µm, preferably such that 50 % of the particles are smaller than 1 µm, even more preferably
smaller than 0.7 µm; further it preferably comprises 25-50 parts in dry weight, preferably
40-60 parts in dry weight of a fine particulate silica pigment, e.g. consisting of
the two silica types as mentioned above.
[0025] In as far as the image receiving coating layer is concerned, according to a further
embodiment of the present invention this layer comprises
100 parts in dry weight of a pigment part consisting of
60 - 100, preferably 60 - 90 parts in dry weight of a fine particulate colloidal silica
pigment; and
0 - 40, preferably 10 - 40 parts in dry weight of a fine particulate polymer pigment;
3 - 6 parts in dry weight of a binder;
0 - 2 parts in dry weight of additives.
[0026] According to a further embodiment of this image receiving coating layer the particulate,
preferably solid or vacuolated polymer pigment in the image receiving coating layer
has a particle size distribution such that more than 90 % of the particles are smaller
than 0.5um, preferably with a particle size distribution such that 90 % of the particles
have sizes between 0.05 and 0.3 µm, in particular between 0.1 and 0.2 µm, or in the
case of a vacuolated polymer pigment also with a mean particle size range of about
0.6 - 1 µm. Indeed it is found that the polymer pigment (biopolymer and/or plastic
pigment) can have a stabilising effect on the rheology of the coating formulation
and it can reduce the shock effect when a cationic additive, e.g. a cationic, preferably
polymeric mordant, is added to the coating formulation.
[0027] A further embodiment of the present invention is characterised in that the binder
part in the image receiving coating layer consists of a PVA-binder, a PVP-binder,
a gelatine binder or mixtures thereof.
[0028] Preferably the image receiving coating layer comprises a mordant for the dyes. In
order not to disturb the anionic (silica) surroundings in this coating the (cationic,
preferably polymeric) mordant content should be as low as possible while still allowing
fixation of the dye. This can be achieved if the mordant is present in 0.1 - 1.5,
preferably 0.5-1.5 parts in dry weight thereof.
[0029] As mentioned above, normally the image receiving coating is directly adjacent to
the pre-coat layer.
[0030] Typically the pre-coat layer has a coating thickness in the range of 5-30 g/m
2 preferably in the range of 10-20 g/m
2, and/or the topcoat layer has a coating thickness in the range of 2-20 g/m
2, preferably of 5-10 g/m
2.
[0031] It is preferred among other reasons for allowing production of the coating layer
is without problems to have a pre-coat formulation essentially free of cationic (e.g.
mordant) components. It is furthermore preferred if the image receiving coating is
transparent.
[0032] As usual, the present coatings can be supplemented with additives, and the additives
in the pre-coat and/or the image receiving coating can be selected from the group
of defoamers, colorants, brighteners, dispersants, thickeners, water retention agents,
preservatives, crosslinkers, lubricants and pH control agents, mordants and mixtures
thereof.
[0033] As mentioned above, the image receiving coating layer (but preferably not at the
pre-coat) may comprise a cationic mordant for the dye as an additive. Beneficially,
this in an amount of 0.1-1.5 parts per dry weight, preferably 0.5-1 parts per dry
weight.
[0034] As mentioned above it is one beneficial element of the proposed coating formulations
that colloidal silica pigment in the image receiving coating layer and/or in the pre-coat
can be an unmodified anionic colloidal silica.
[0035] As also mentioned above, the fine particulate calcium carbonate pigment in the pre-coat
can be a precipitated calcium carbonate pigment, preferably a needle-shaped type and/or
an anionic type. It may also be of the above-mentioned fine particulate ground calcium
carbonate type with surface and internal structure modification.
[0036] The end paper can have a gloss above or equal to 45% according 75°DIN, preferably
above or equal to 50%, even more preferably above or equal to 55%, so very high-gloss
levels can be achieved especially after calendering.
[0037] Furthermore, as stated above, the present invention relates to a method for producing
an inkjet paper as given above. Preferentially, this method is characterised in that
in a first step the pre-coat formulation is applied to the paper substrate with a
solids content above 40%, preferably in the range of 50-60%, most preferably in the
range of 50-55%, and wherein subsequently in a second step the image receiving coating
layer formulation is applied with a solids content above or equal to 40%, preferably
between 40 and 55%, most preferably between 40 and 50%. Indeed it is one of the unexpected
but highly beneficial advantages of the proposed coating formulation that in contrast
to the coating formulations according to the state-of-the-art for such types of inkjet
papers, the coating formulations can be applied with a relatively high solids content
allowing high production speed and low drying efforts. Preferentially, the formulations
are applied using blade coating, rod coating, air knife coating, curtain coating,
preferably blade coating with a speed of more than 600 m/min, preferably with a speed
of more than 800 m/min, even more preferably with a speed of at least 900 m/min.
[0038] For a glossy paper, after application of the two coating layers the paper can be
calendered.
[0039] Further embodiments of the present invention are outlined in the dependent claims.
[0040] To summarize, the following main aspects of the invention emerge:
The concept of the new ink jet paper is containing at least two coating layers: one
pre-coating layer which is the absorptive layer and one top coating layer which is
providing gloss and both layers synergistically enhancing printing properties.
[0041] The obtained coated paper will dry quickly after printing on common ink jet printers
and have a high gloss level (up to or even above 55% according DIN75). The coating
will be porous contrary to a large part of glossy inkjet papers.
[0042] In the pre-coating layer a typical recipe is as given in Table 1:
Table 1, Precoat layer
| |
Parts |
| PCC (e.g. Opacarb A60) |
50 |
| Colloidal silica (e.g. Ludox PW50) |
20 |
| Silica gel (e.g. Syloid 803) |
30 |
| Non-latex-binder, preferably PVP-binder (e.g. PVP or Luvitec K30) |
6 |
| Latex binder (e.g. Eurolatex L0607) |
4 |
| Additives, e.g. optical brightener |
0.5 |
[0043] The Opacarb pigment is a fine PCC is available from SMI (Specialty Minerals Inc.,
USA). It can be replaced with GCC, other PCC types.
[0044] The Ludox PW50 is a colloidal silica available from Grace Davison, USA. In this recipe
any colloidal silica can be used.
[0045] Syloid C803 is a porous silica gel pigment available from Grace Davison, USA. It
can be replaced by other anionic porous pigments such as other silica gel types, the
above-mentioned fine particulate ground calcium carbonate type with surface and internal
structure modification, alumino silicates, PCC, calcined clay. This pigment provides
the main porosity of the coating layer. It can be used from 10 to 50 parts in the
coating.
[0046] PVP or Luvitec K30 is a polyvinyl pyrolidone binder e.g. available from ISP or BASF
(DE). In this recipe it is a binder and dye mordant. It can be replaced by other binder
types such as polyvinyl alcohol or other PVP grades and copolymers, gelatines.
[0047] Eurolatex L0607 is a SB latex of supplier EOC. It can be replaced with other latexes
(SB or acrylate type).
[0048] The solids content of the pre coating recipe is maximized. Solids levels are typically
between 50 and 55%, preferably between 50 and 60%.
[0049] Note that preferably there is no cationic aid used in the pre-coating layer as opposed
to other inkjet receiving layers. The coating layer hereby stays essentially completely
anionic.
[0050] Colour density in the coating layer is obtained by using a combination of colloidal
silica and PVP with the PCC.
[0051] The coating composition can be applied by any number of well known techniques such
as blade coating, rod coating, air knife coating, curtain coating. Specific for this
coating is that due to the high solids content it can be coated at high speeds typically
900m/min or higher e.g. with the blade coater.
[0052] The coating thickness can be from 5 till 30 gsm per side but is preferably from 10-20
gsm.
[0053] For a top coating recipe a typical recipe is as given in Table 2:
Table 2: Image receiving coating layer
| |
Parts |
| Colloidal silica (e.g. Ludox PW50) |
80 |
| Plastic pigment (e.g. DPP 3710) |
20 |
| Binder (e.g. Mowiol 4-88) |
4 |
| Dye mordant (e.g. Induquat ECR 35 L or Cartafix VXU) |
1 |
[0054] The top coating layer is highly porous to obtain a fast flow of the inkjet fluids
to the absorptive pre-coating.
[0055] The Ludox PW50 is colloidal silica. In this recipe any anionic colloidal silica can
be used.
[0056] DPP 3710 is a plastic pigment particle available from Dow Chemicals. It provides
high gloss levels and can be replaced with other plastic pigment types.
[0057] Mowiol 4-88 is a PVOH based binder available from Kuraray. It can be replaced with
other hydrophilic binders such as PVP, gelatine. It can be used from 0 to 20 parts.
[0058] Optionally Induquat ECR35L available from Indulor Chemie or Cartafix VXU from Clariant
is used as a cationic mordant (poly-DADMAC). It can be used from 0.1 to 1.5 parts.
It can be replaced/supplemented with other mordant types.
[0059] The amount of mordant in the coating recipe can be kept low to keep the total coating
recipe in an overall anionic state.
[0060] The solids content of the top coating recipe is maximized. Solids levels are typically
between 40 and 50%, preferably between 40 and 55%.
[0061] The top coating composition can be applied by any number of well known techniques
such as blade coating, rod coating, air knife coating, curtain coating. Specific for
this coating is that due to the high solids content it can be coated at high speeds
typically 900m/min or higher, preferably with a blade coater.
[0062] The coating yield for the top coating can be from 2 till 20 gsm per side but is preferably
from 5-10 gsm.
SHORT DESCRIPTION OF THE FIGURES
[0063] In the accompanying drawings preferred embodiments of the invention are shown in
which:
- Figure 1
- shows the colour density of end paper on three different printer types; and
- Figure 2
- shows the colour gamut of end paper on three different printer types.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0064] A new coating development has lead to a coating recipe that shows good inkjet printability,
quick ink drying and high gloss. This coating can be applied with blade at high speeds
and is overall anionic of nature. The development is consisting of a special pre-coating
layer in combination with a highly porous top coating layer. After calendering the
coating can be printed on a variety of commercial ink-jet printers with different
settings to become photo quality prints with lifelike colours. High gloss levels can
be obtained while maintaining enough porosity for the inkjet printability of the medium.
Colour gamut and optical density are on the accepted high level of commercial papers.
[0065] In the inkjet industry it is common knowledge that the best way to have high optical
densities is to use a mordant for the dyes. These mordants are cationic polymers which
are also used for water fastness of the prints. It is easy to use this kind of polymers
when all the other pigments in the coating bear the same charge, thus are being cationic
(e.g. as detailed in
WO 01/45956). In regular pigmented inkjet papers this is not an issue since alumina is a cationic
pigment by nature and silicas are available in cationic grades as well.
[0066] In our concept however we are using standard PCC's or the above-mentioned fine particulate
ground calcium carbonate type with surface and internal structure modification and
unmodified colloidal and other silica particles. These are all anionic by charge and
therefore the mixing process with cationic polymers is very difficult. When only as
little as 1 part of cationic polymer is added to a PCC slurry a heavy agglomeration
caused by a shock effect is very often observed. This shock effect is due to the zero
charge of the mixture at that moment. Overdosing of cationic polymers leads to a cationic
coating which is not an option since this might cause shock effects with regular produced
anionic coatings commonly run for offset purposes when changing the coating formulations
on the machine.
[0067] Therefore the proposal here is to add low amounts of cationic polymers to the coating,
resulting in a unique overall anionic ink jet coating concept. Upon wetting with the
inkjet fluids these polymers will still be able to bind the anionic dyes and provide
further improved colours of the prints.
[0068] The results from laboratory trials led to a preferred formulation with just one pre-coating
and one top coating recipe as given in Table 3.
Table 3: coating formulation, P=Pre-coat, T=Topcoating
| |
P5 |
T5 |
| Pigments |
|
|
| Opacarb A 60 |
50,00 |
|
| Ludox PW 50 |
20,00 |
80,00 |
| Syloid C 803 |
30,00 |
|
| DPP 3710 |
|
20,00 |
| PVP K 30 |
6,00 |
|
| Mowiol 4-88 |
4,00 |
4,00 |
| Litex 7110 |
4,00 |
|
| Induquat ECR 35 L |
|
1,00 |
| Final solids of coating (%) |
55 |
48 |
[0069] The pre-coat layer was applied at 17 gsm and the top coating layer at 8 gsm. In this
way coating machine speed of up to 900 m/min were possible. The paper was calendered
to a gloss level of 55% or 55.6% according 75°DIN.
[0070] The optical density and the colour gamut of such papers is given in Figure 1 and
2, respectively, for three different ink jet printer types (a: Epson R200, b: Canon
4200, c: HP 5150), respectively. As comparative example commercial paper HP Everyday
was used.
[0071] This paper does show the right optical density levels and has vivid colours. It shows
no bleed at Epson, HP and the Canon.
[0072] Overall the colours are vivid and bright, optical density levels are high, especially
in CMY the optical density of this paper is higher than the HP Everyday paper. As
it shows from the graphs the colour gamut in total is larger compared to the colour
gamut of the HP Everyday paper.
[0073] The paper could produce photo quality prints on various pre-installed settings for
photo paper on various printers, also photo printing software packages delivered with
the printer can be used for good quality prints.
[0074] The paper was also tested on a commercial large format printer The prints produced
were clear and sharp.
[0075] So the current invention preferably contains two coating layers: a pre-coating and
a top coating as follows:
Pre-coating:
[0076] Main pre-coat components: colloidal silica and PVP are supposed to actually fix the
dyes;
Colloidal silica such as Ludox PW50 equal/above 10 pph; inter-particle porosity provides
(additional) absorptivity ; can be fully or partially replaced by the above-mentioned
fine particulate ground calcium carbonate type with surface and internal structure
modification;
Carbonate such as PCC Opacarb A60 can be replaced by e.g. GCC like Covercarb 75; possible
range of these carbonates 20-75, preferred 40-60 pph;
Silica gel such as Syloid C803 gives additional porosity; can be fully or partially
be replaced by the above-mentioned fine particulate ground calcium carbonate type
with surface and internal structure modification;
Binder such as Litex 7110 and/or Eurolatex L0607 essentially needed for improved adhesion
of coating layers to substrate;
PVP role as dye mordant (and binder) and its seemingly limited cationogenity related
to mesomeric/resonance mechanism;
Solids content of new pre-coat 50-55% versus about 10-30% for regular ink jet coating;
The pre-coating is thus preferentially consisting out of:
Opacarb A60: Fine PCC needle-shaped: provides porosity;
Ludox PW50: fine colloidal silica: provides absorptivity and improved colour density
of the prints;
Syloid C 803: porous silica: provides improved liquid absorption and buffer volume;
PVP K 30: binder against colour fading, improved colour density;
Litex 7110: SB-latex: provides improved fixation of the coating layer;
Top coating:
[0077] Top coating layer is preferably transparent.
[0078] The top coating is thus preferably consisting out of:
Ludox PW50: fine colloidal silica: gloss and porosity, transparent;
DPP3710: fine solid sphere plastic pigment: reduce shock effects, provides (additional)
gloss;
Mowiol 4-88: binder: protective colloid for cationic mordant;
Induquat ECR35L: mordant: improved colour density, dye fixative;
Common issues for both coating:
[0079] Solids content of new pre-coat (practically) 50-55% and topcoat 48-50%, normally
50% max. versus about only 10-30% for regular ink jet coating; allows high coating
application speeds up to 900 - 1100 m/min.
[0080] Quick dry behaviour of new ink jet paper: faster than regular 'swellable type' ink
jet papers and about equally fast as porous (cationic and expensive alumina based)
ink jet papers in market. No actual drying speed data according specific test available.
Based on perception/observations: the printed paper can be touched immediately after
removing it from the print tray.
[0081] Other apparent advantages of new concept: a) extra feature = can on paper be regularly
coated and printed at two sides (uncommon in case of regular ink jet papers).
1. Method for producing an inkjet paper comprising at least one image receiving coating
layer and at least one pre-coat layer beneath said image receiving coating layer on
a paper substrate, wherein
the pre-coat layer comprises
100 parts in dry weight of a pigment part consisting of 20-75 parts in dry weight
of a fine particulate calcium carbonate and/or kaolin;
10 - 70 parts in dry weight of a fine particulate silica and/or of a fine particulate
ground calcium carbonate with surface and internal structure modification as a result
of treatment with one or more medium to strong H3O+ ion providers and optionally with additional treatment of gaseous carbon dioxide;
and
0 - 30 parts of additional fine particulate pigments
4 - 20 parts in dry weight of a binder part
0-6 parts in dry weight of additives;
and the image receiving coating layer comprises
100 parts in dry weight of a pigment part consisting of 50 - 100 parts in dry weight
of a fine particulate silica; and
0 - 50 parts in dry weight of a fine particulate polymer pigment; and
0 - 30 parts of additional fine particulate pigments
2-10 parts in dry weight of a binder
0-3 parts in dry weight of additives.,
wherein in a first step the pre-coat formulation is applied to the paper substrate
with a solids content above 40% and wherein subsequently in a second step the image
receiving coating layer formulation is applied with a solids content above or equal
to 40%.
2. Method according to claim 1, wherein the pre-coat formulation is applied to the paper
substrate with a solids content in the range of 50-60%, preferably in the range of
50-55%, wherein preferably the formulation is applied using blade coating, rod coating,
air knife coating, curtain coating.
3. Method according to any of the preceding claims, wherein the image receiving coating
layer formulation is applied with a solids content between 40-55%, preferably between
40 and 50%, wherein preferably the formulation is applied using blade coating, rod
coating, air knife coating, curtain coating, and wherein preferably after application
of the two coating layers the paper is calendered.
4. Method according to any of the preceding claims, wherein at least one of the formulations
is applied using blade coating with a speed of more than 600 m/min, preferably with
a speed of more than 800 m/min, even more preferably with a speed of at least 900
m/min.
5. Method according to any of the preceding claims, wherein the pre-coat and/or the receiving
coating formulations are in an overall anionic state.
6. Ink jet paper, made using a method according to any of the preceding claims, comprising
at least one image receiving coating layer and at least one pre-coat layer beneath
said image receiving coating layer on a paper substrate, wherein
the pre-coat layer comprises
100 parts in dry weight of a pigment part consisting of
20-75 parts in dry weight of a fine particulate calcium carbonate and/or kaolin;
10 - 70 parts in dry weight of a fine particulate silica and/or of a fine particulate
ground calcium carbonate with surface and internal structure modification as a result
of treatment with one or more medium to strong H3O+ ion providers and optionally with additional treatment of gaseous carbon dioxide
and
0 - 30 parts of additional fine particulate pigments
4 - 20 parts in dry weight of a binder part
0-6 parts in dry weight of additives;
and the image receiving coating layer comprises
100 parts in dry weight of a pigment part consisting of
50 - 100 parts in dry weight of a fine particulate silica; and
0 - 50 parts in dry weight of a fine particulate polymer, such as plastic and/or biopolymer,
pigment; and
0 - 30 parts of additional fine particulate pigments
2 - 10 parts in dry weight of a binder
0-3 parts in dry weight of additives.
7. Ink jet paper according to claim 6, wherein the pre-coat layer comprises 100 parts
in dry weight of a pigment part consisting of
40-75 parts in dry weight, preferably 50-60 parts in dry weight, of a fine particulate
ground or precipitated calcium carbonate;
25-70 parts in dry weight, preferably 40-60 parts in dry weight of a fine particulate
silica pigment and/or of a fine particulate ground calcium carbonate with surface
and internal structure modification as a result of treatment with one or more medium
to strong H3O+ ion providers and optionally with additional treatment of gaseous carbon dioxide
wherein preferably the fine particulate silica pigment in the pre-coat layer is composed
of 5 - 50, preferably 10-50 parts in dry weight of a colloidal silica and 10-40 parts
in dry weight of a silica gel,
and wherein more preferably the fine particulate silica pigment in the pre-coat layer
is composed of 10 - 30, preferably 15-30 parts in dry weight of a colloidal silica
and of 20 - 35, preferably 25-35 parts in dry weight of a silica gel and wherein even
more preferably the silica gel in the pre-coat layer has a particle size distribution
such that the average particle size is in the range of 0.1-10 µm, preferably below
7 µm and most preferably below 4.0 µm and/or the colloidal silica in the pre-coat
layer has a particle size distribution such that the average particle size is in the
range of 10 - 120 nm, preferably 40 - 100 nm.
8. Inkjet paper according to any of the claims 6 - 7, wherein the binder part in the
pre-coat layer comprises a latex binder and a second binder selected from the group
of polyvinyl pyrrolidone binder, PVA, gelatine and mixtures thereof, wherein more
preferably the binder part comprises 2-20, preferably 2-14 parts in dry weight of
a latex binder, preferably a styrene butadiene-binder and 2-8, preferably 4-8 parts
in dry weight of a polyvinyl pyrrolidone binder, preferably of polyvinyl pyrrolidone
with a molecular weight of more than 20'000 Da, even more preferably of more than
30'000 Da, most preferably in the range of 40'000 Da - 80'000 Da.
9. Inkjet paper according to any of the claims 6-8, wherein the pre-coat layer comprises
100 parts in dry weight of a pigment part consisting of 50-75 parts in dry weight,
preferably 40-60 parts in dry weight, of a fine particulate ground or precipitated
calcium carbonate, wherein the fine particulate calcium carbonate has a particle size
distribution such that 50 % of the particles are smaller than 1 µm, preferably smaller
than 0.7 µm;
25-50 parts in dry weight, preferably 40-60 parts in dry weight of a fine particulate
silica pigment and/or of a fine particulate ground calcium carbonate with surface
and internal structure modification as a result of treatment with one or more medium
to strong H3O+ ion providers and optionally with additional treatment of gaseous carbon dioxide.
10. Inkjet paper according to any of the claims 6-9, wherein the image receiving coating
layer comprises
100 parts in dry weight of a pigment part consisting of
60 - 100, preferably 60 - 90 parts in dry weight of a fine particulate colloidal silica
pigment; and
0 - 40, preferably 10 - 40 parts in dry weight, preferably 10-30 parts in dry weight,
of a fine particulate polymer pigment;
3 - 6 parts in dry weight of a binder
0-2 parts in dry weight of additives.
11. Inkjet paper according to claim 10, wherein the particulate, preferably solid or vacuolated
polymer pigment in the image receiving coating layer has a particle size distribution
such that more than 90 % of the particles are smaller than 0.5um, preferably with
a particle size distribution such that 90 % of the particles have sizes between 0.05
and 0.3 µm, in particular between 0.1 and 0.2 µm, or in the case of a vacuolated polymer
pigment also with a mean particle size of about 0.6-1 µm.
12. Inkjet paper according to any of the claims 6 - 11, wherein the binder part in the
image receiving coating layer consists of a PVA-binder, a PVP-binder, a gelatine binder
or mixtures thereof
and/or wherein the image receiving coating layer comprises a mordant for the dyes,
preferably 0.1-1.5, preferably 0.5-1.5 parts in dry weight thereof
and/or wherein the image receiving coating is directly adjacent to the pre-coat layer
and/or wherein the pre-coat layer has a coating thickness in the range of 5-30 g/m2, preferably in the range of 10-20 g/m2, and wherein the topcoat layer has a coating thickness in the range of 2-20 g/m2, preferably of 5-10 g/m2.
and/or wherein the pre-coat formulation is essentially free of cationic components
and/or wherein the overall coating charge is anionic
and/or wherein the image receiving coating is transparent
and/.or wherein the additives in the pre-coat and/or the image receiving coating are
selected from the group of defoamers, colorants, brighteners, dispersants, thickeners,
water retention agents, preservatives, crosslinkers, lubricants and pH control agents
and mixtures thereof
and/or wherein the image receiving coating layer comprises a cationic mordant for
the dye as an additive in an amount of 0.1-1.5 parts per dry weight, preferably 0.5-1
parts per dry weight
and/or wherein the pre-coat layer is essentially free of cationic mordant additives.
13. Inkjet paper according to any of the claims 6-12, wherein the colloidal silica pigment
in the image receiving coating layer is a unmodified anionic colloidal silica
and/or wherein the fine particulate calcium carbonate pigment in the pre-coat is a
precipitated calcium carbonate pigment, preferably a needle-shaped type and/or an
anionic type.
14. Inkjet paper according to any of the claims 6 - 13, wherein the end paper has a gloss
above or equal to 45% according 75°DIN, preferably above or equal to 50%, even more
preferably above or equal to 55%.
15. Inkjet paper according to any of the claims 6 - 14, wherein the pre-coat and/or the
receiving coating layer(s) are overall anionic.
1. Verfahren zur Herstellung eines Papiers für Tintenstrahl umfassend mindestens eine
bildaufnehmende Beschichtungsschicht und mindestens eine Vorbeschichtungsschicht unterhalb
besagter bildaufnehmender Beschichtungsschicht auf einem Papiersubstrat, wobei die
Vorbeschichtungsschicht
100 Trockengewichtsanteile eines Pigmentanteils bestehend aus
20-75 Trockengewichtsanteile eines feinen, teilchenförmigen Kalziumkarbonats und/oder
Kaolins;
10 - 70 Trockengewichtsanteile eines feinen, teilchenförmigen Silikas und/oder eines
feinen, teilchenförmigen, gemahlenen Kalziumkarbonats mit einer, aus einer Behandlung
mit einem oder mehreren, mittleren bis starken H3O+-Ionenlieferanten, und wahlweise
aus zusätzlicher Behandlung mit gasförmigem Kohlenstoffdioxid resultierenden Modifikation
der Oberfläche oder inneren Struktur; und
0 - 30 Anteilen eines zusätzlichen feinen, teilchenförmigen Pigments
4 - 20 Trockengewichtsanteilen eines Bindemittelanteils
0-6 Trockengewichtsanteile eines Additivs;
umfasst,
und die bildaufnehmende Beschichtungsschicht
100 Trockengewichtsanteile eines Pigmentanteils bestehend aus
50 - 100 Trockengewichtsanteile eines feinen, teilchenförmigen Silikas; und
0 - 50 Trockengewichtsanteile eines feinen, teilchenförmigen Polymerpigments; und
0 - 30 Anteilen eines zusätzlichen feinen, teilchenförmigen Pigments
2 - 10 Trockengewichtsanteile eines Bindemittels
0-3 Trockengewichtsanteile eines Additivs;
umfasst,
wobei in einem ersten Schritt die Formulierung der Vorbeschichtungsschicht mit einem
Trockenanteil von oberhalb von 40% auf das Papiersubstrat aufgetragen wird und wobei
anschliessend in einem zweiten Schritt die Formulierung der bildaufnehmende Beschichtungsschicht
mit einem Trockenanteil von oberhalb von, oder gleich, 40% aufgetragen wird.
2. Verfahren gemäss Anspruch 1, wobei die Formulierung der Vorbeschichtungsschicht mit
einem Feststoffanteil im Bereich von 50-60%, bevorzugt im Bereich von 50-55% auf das
Papiersubstrat aufgetragen wird wobei die Formulierung bevorzugt anhand eines Rakelstreichverfahrens,
Stabstreichverfahrens, Luftbürstenstreichverfahrens, Giessstreichverfahrens aufgetragen
wird.
3. Verfahren gemäss irgendeinem der vorangehenden Ansprüche, wobei die Formulierung der
bildaufnehmenden Beschichtungsschicht mit einem Feststoffanteil zwischen 40-55%, bevorzugt
zwischen 40 und 50% aufgetragen wird, wobei die Formulierung bevorzugt anhand Rakelstreichverfahrens,
Stabstreichverfahrens, Luftbürstenstreichverfahrens, Giessstreichverfahrens aufgetragen
wird, und wobei bevorzugt nach Auftragen der zwei Beschichtungsschichten das Papier
kalandriert wird.
4. Verfahren gemäss irgendeinem der vorangehenden Ansprüche, wobei mindestens einer der
Formulierungen anhand eines Rakelstreichverfahrens aufgetragen wird, mit einer Geschwindigkeit
von mehr als 600 m/min, bevorzugt mit einer Geschwindigkeit von mehr als 800 m/min,
sogar bevorzugter mit einer Geschwindigkeit von mindestens 900 m/min.
5. Verfahren gemäss irgendeinem der vorangehenden Ansprüche, wobei die Vorbeschichtung
und/oder die Formulierung der aufnehmenden Beschichtung in einem gesamthaft anionischen
Zustand befinden.
6. Papier für Tintenstrahl, bevorzugt anhand des Verfahrens gemäss irgendeinem der vorangehenden
Ansprüche hergestellt, umfassend mindestens eine bildaufnehmende Beschichtungsschicht
und mindestens eine Vorbeschichtungsschicht unterhalb besagter bildaufnehmenden Beschichtungsschicht
auf einem Papiersubstrat, wobei
die Vorbeschichtungsschicht
100 Trockengewichtsanteile eines Pigmentanteils, bestehend aus
20-75 Trockengewichtsanteilen eines feinen, teilchenförmigen Kalziumkarbonats und/oder
Kaolin;
10-70 Trockengewichtsanteilen eines feinen, teilchenförmigen Silikas und/oder eines
feinen, teilchenförmigen, gemahlenen Kalziumkarbonats mit einer, aus einer Behandlung
mit einem oder mehreren, mittleren bis starken H3O+-Ionenlieferanten, und wahlweise
aus zusätzlicher Behandlung mit gasförmigem Kohlenstoffdioxid resultierenden Modifikation
der Oberfläche oder inneren Struktur,
0 - 30 Anteilen eines zusätzlichen feinen, teilchenförmigen Pigments,
4 - 20 Trockengewichtsanteile eines Bindemittelanteils
0-6 Trockengewichtsanteile eines Additivs; umfasst
und die bildaufnehmende Beschichtungsschicht
100 Trockengewichtsanteile eines Pigmentanteils, bestehend aus
50 - 100 Trockengewichtsanteilen eines feinen, teilchenförmigen Silikas; und
0 - 50 Trockengewichtsanteilen eines feinen, teilchenförmigen Polymers, wie Kunststoff-
und/oder Biopolymerpigment; und
0 - 30 Anteilen eines zusätzlichen feinen, teilchenförmigen Pigments
2 - 10 Trockengewichtsanteile Bindemittel
0-3 Trockengewichtsanteilen eines Additivs; umfasst.
7. Papier für Tintenstrahl gemäss Anspruch 6, wobei die Vorbeschichtungsschicht 100 Trockengewichtsanteile
eines Pigmentanteils umfasst, bestehend aus
40-75 Trockengewichtsanteilen, bevorzugt 50-60 Trockengewichtsanteilen, eines feinen,
gemahlenen oder gefällten Kalziumkarbonats;
25-70 Trockengewichtsanteilen, bevorzugt 40-60 Trockengewichtsanteile eines feinen,
teilchenförmigen, Silikapigments und/oder eines feinen, teilchenförmigen, gemahlenen
Kalziumkarbonats mit einer, aus einer Behandlung mit einem oder mehreren, mittleren
bis starken H3O+-Ionenlieferanten, und wahlweise aus zusätzlicher Behandlung mit gasförmigem
Kohlenstoffdioxid resultierenden Modifikation der Oberfläche oder inneren Struktur,
wobei bevorzugt das feine, teilchenförmige Silikapigment in der Vorbeschichtungsschicht
aus 5-50, bevorzugt 10-50 Trockengewichtsanteilen eines Kolloid-Silikas und 10-40
Trockengewichtsanteilen eines Silika-Gels besteht,
und wobei bevorzugter das feine, teilchenförmige Silikapigment in der Vorbeschichtungsschicht
aus 10-30, bevorzugt 15-30Trockengewichtsanteilen eines Kolloid-Silikas und 20 - 35,
bevorzugt 25-35 Trockengewichtsanteilen eines Silika-Gel besteht,
und wobei sogar bevorzugter das Silika-Gel in der Vorbeschichtungsschicht eine Teilchengrössenverteilung
hat, so dass die durchschnittliche Teilchengrösse im Bereich von 0.1-10 um, bevorzugt
unterhalb 7 um und am bevorzugtesten unterhalb 4.0 um liegt und/oder das Kolloid-Silika
in der Vorbeschichtungsschicht eine Teilchengrössenverteilung hat, so dass die durchschnittliche
Teilchengrösse im Bereich von 10 - 120 nm, bevorzugt 40 -100 nm liegt.
8. Papier für Tintenstrahl gemäss irgendeinem der Ansprüche 6 - 7, wobei der Bindemittelanteil
in der Vorbeschichtungsschicht ein Latex-Bindemittel und ein zweites Bindemittel umfasst,
ausgesucht aus der Gruppe von Polyvinyl-Pyrrolidon-Bindemittel, PVA, Gelatine und
Mischungen hiervon, wobei bevorzugter der Bindemittelanteil 2-20, bevorzugt 2-14 Trockengewichtsanteile
an Latex-Bindemittel, bevorzugt ein Styrene-Butadiene-Bindemittel und 2-8, bevorzugt
4-8 Trockengewichtsanteile an Polyvinyl-Pyrrolidon-Bindemittel, bevorzugt an Polyvinyl-Pyrrolidon
mit einer Molekuargewicht von mehr als 20'000 Da, sogar bevorzugter von mehr als 30'000
Da, am bevorzugtesten im Bereich von 40'000 Da - 80'000 Da, umfasst.
9. Papier für Tintenstrahl gemäss irgendeinem der Ansprüche 6-8, wobei die Vorbeschichtungsschicht
100 Trockengewichtsanteile eines Pigmenanteils, bestehend aus
50-75 Trockengewichtsanteilen, bevorzugt 40-60 Trockengewichtsanteilen, eines feinen,
gemahlenen oder gefällten Kalziumkarbonats, wobei das feine, gemahlene Kalziumkarbonat
eine Teilchengrössenverteilung hat, so dass 50 % der Teilchen kleiner als 1 um, bevorzugt
kleiner als 0.7 um sind;
25-50 Trockengewichtsanteilen, bevorzugt 40-60 Trockengewichtsanteile eines feinen
teilchenförmigen Silikapigments und/oder eines feinen, teilchenförmig, gemahlenen
Kalziumkarbonats mit einer, aus einer Behandlung mit einem oder mehreren, mittleren
bis starken H3O+-Ionenlieferanten, und wahlweise aus zusätzlicher Behandlung mit gasförmigem
Kohlenstoffdioxid resultierenden Modifikation der Oberfläche oder inneren Struktur,
umfasst.
10. Papier für Tintenstrahl gemäss irgendeinem der Ansprüche 6 - 9, wobei die bildaufnehmende
Beschichtungsschicht
100 Trockengewichtsanteile eines Pigmentanteils, bestehend aus
60 - 100, bevorzugt 60 - 90 Trockengewichtsanteilen eines feinen, teilchenförmigen
Kolloid-Silikapigments; und
0 - 40, bevorzugt 10 - 40 Trockengewichtsanteilen, bevorzugt 10-30 Trockengewichtsanteilen,
eines feinen, teilchenförmigen Polymerpigments;
3 - 6 Trockengewichtsanteilen eines Bindemittels;
0-2 Trockengewichtsanteilen eines Additivs,
umfasst.
11. Papier für Tintenstrahl gemäss Anspruch 10, wobei das teilchenförmige, bevorzugt volle
oder vakuolierte Polymerpigment in der bildaufnehmenden Beschichtungsschicht eine
Teilchengrössenverteilung hat, so dass mehr als 90 % der Teilchen keiner als 0.5 um
sind, bevorzugt mit einer Teilchengrössenverteilung so dass 90 % der Teilchen Grössen
zwischen 0.05 und 0.3 um, insbesondere zwischen 0.1 und 0.2 um sind, oder im Fall
eines vakuolierten Polymerpigments auch mit einer mittleren Teilchengrösse von etwa
0.6 -1 um.
12. Papier für Tintenstrahl gemäss irgendeinem der Ansprüche 6 - 11, wobei der Bindemittelanteil
in der bildaufnehmenden Beschichtungsschicht aus einem PVA-Bindemittel, einem PVP-Bindemittel,
einem Gelatine-Bindemittel oder Mischungen hiervon besteht,
und/oder wobei die bildaufnehmende Beschichtungsschicht ein Farbstoffbeizmittel, bevorzugt
0.1-1.5, bevorzugt 0.5 - 1.5 Trockengewichtsanteilen hiervon umfasst
und/oder wobei bildaufnehmenden Beschichtung direkt angrenzend zu der Vorbeschichtungsschicht
ist,
und/oder wobei die Vorbeschichtungsschicht eine Beschichtungsdicke im Bereich von
5-30 g/m2, bevorzugt im Bereich von 10-20 g/m2 hat , und wobei die Oberbeschichtungsschicht eine Beschichtungsdicke im Bereich von
2-20 g/m2, bevorzugt von 5-10 g/m2 hat,
und/oder wobei die Formulierung der Vorbeschichtung im Wesentlichen frei von kationischen
Komponenten ist und/oder wobei die allgemeine Ladung der Beschichtung anionisch ist,
und/oder wobei die bildaufnehmende Beschichtung transparent ist,
wobei die Additive im der Vorbeschichtung und/oder in der bildaufnehmenden Beschichtung
ausgesucht sind aus der Gruppe der Entschäumer, Farbmittel, Aufheller, Dispergiermittel,
Verdickungsmittel, Wasserretentionsmittel, Konservierungsmittel, Vernetzungsmittel,
Schmiermittel, und pH-Kontrollmittel und Mischungen hiervon,
und/oder wobei die bildaufnehmende Beschichtungsschicht ein kationisches Farbstoffbeizmittel
als Additiv in einer Menge von 0.1-1.5 Trockengewichtsanteilen, bevorzugt 0.5-1 Trockengewichtsanteilen
umfasst,
und/oder wobei die Vorbeschichtungsschicht im Wesentlichen frei von kationischen Beizmittel
Additiven ist.
13. Papier für Tintenstrahl gemäss irgendeinem der Ansprüche 6-12, wobei das Kolloid-Silikapigment
in der bildaufnehmenden Beschichtungsschicht ein unmodifiziertes anionische Kolloidal-Silika
ist
und/oder wobei das feine, teilchenförmige Kalziumkarbonatpigment in der Vorbeschichtung
ein gefälltes Kalziumkarbonatpigment ist, bevorzugt ein nadelförmiger Typ und/oder
anionischer Typ.
14. Papier für Tintenstrahl gemäss irgendeinem der Ansprüche 6 - 13, wobei das Endpapier
einen Glanz oberhalb von, oder gleich, 45% gemäss 75°DIN, bevorzugt oberhalb von,
oder gleich, 50%, sogar bevorzugter oberhalb von, oder gleich, 55% hat.
15. Papier für Tintenstrahl gemäss irgendeinem der Ansprüche 6 - 14, wobei die Vorbeschichtung
und/oder die bildaufnehmende(n) Beschichtungsschicht(en) allgemein anionisch sind.
1. Méthode pour la production d'un papier à jet d'encre comprenant au moins une couche
de revêtement récepteur d'image et au moins une couche de pré-revêtement sous ladite
couche de revêtement récepteur d'image sur un papier substrat, dans laquelle
la couche de pré-revêtement comprend
100 parties en poids sec d'une partie de pigment se composant de
20-75 parties en poids sec d'un carbonate de calcium et/ou kaoline particulaire fin;
10 - 70 parties en poids sec d'un silice particulaire fin et/ou d'un carbonate de
calcium particulaire fin moulu avec modification de surface et structure interne résultante
d'un traitement avec un ou plusieurs fournisseurs moyens à forts de ions H3O+ et optionnellement
avec un traitement supplémentaire au dioxyde de carbone gazeux; et
0 - 30 parties de pigments particulaires fins supplémentaires,
4 - 20 parties en poids sec d'une partie de liant
0-6 parties en poids sec d'additifs;
et la couche de revêtement récepteur d'image comprend
100 parties en poids sec d'une partie de pigment se composant de
50 - 100 parties en poids sec d'une silice particulaire fine; et
0 - 50 parties en poids sec d'un pigment polymère particulaire fin;
et
0 - 30 parts de pigments supplémentaires particulaires fins
2 - 10 parties en poids sec d'un liant,
0-3 parties en poids sec of additives,
dans laquelle, dans une première étape, la formulation de pré-revêtement est appliquée
au papier substrat avec un contenu de solides au-delà de 40% et dans laquelle subséquemment,
dans une deuxième étape, la formulation de couche de revêtement récepteur d'image
est appliquée avec un contenu de solides au-delà de, ou égal à, 40%.
2. Méthode selon la revendication 1, dans laquelle la formulation de pré-revêtement est
appliquée au papier substrat avec un contenu de solides dans le domaine de 50-60%,
préférablement dans le domaine de 50-55%, dans laquelle préférablement la formulation
est appliquée en utilisant le couchage à racle, couchage à barre, couchage à lame
d'air, couchage à rideau.
3. Méthode selon l'une quelconque des revendications précédentes, dans laquelle la formulation
de couche de revêtement récepteur d'image est appliquée avec un contenu de solides
entre 40-55%, préférablement entre 40 et 50%, dans laquelle préférablement la formulation
est appliquée en utilisant le couchage à racle, couchage à barre, couchage à lame
d'air, couchage à rideau, et dans laquelle préférablement après l'application des
deux couches de revêtement, le papier est calandré.
4. Méthode selon l'une quelconque des revendications précédentes, dans laquelle au moins
une des formulations est appliquée en utilisant le couchage à racle avec une vitesse
supérieure à 600 m/min, préférablement avec une vitesse supérieure à 800 m/min, même
plus préférablement avec une vitesse d'au moins 900 m/min.
5. Méthode selon l'une quelconque des revendications précédentes, dans laquelle le pré-revêtement
et/ou les formulations de revêtement récepteur sont dans un état généralement anionique.
6. Papier à jet d'encre, préférablement élaboré en utilisant la méthode selon l'une quelconque
des revendications précédentes, comprenant au moins une couche de revêtement récepteur
d'image et au moins une couche de pré-revêtement sous ladite couche de revêtement
récepteur d'image sur un papier substrat, dans lequel
la couche de pré-revêtement comprend
100 parties en poids sec d'une partie de pigment se composant de
20-75 parties en poids sec d'un carbonate de calcium et/ou kaoline particulaire fin;
10 - 70 parties en poids sec d'une silice particulaire fine et/ou d'un carbonate de
calcium particulaire fin moulu avec modification de surface et structure interne résultante
d'un traitement avec un ou plusieurs fournisseurs moyens à forts de ions H3O+ et optionnellement
avec un traitement supplémentaire au dioxyde de carbone gazeux et
0 - 30 parties de pigments particulaires fins supplémentaires
4 - 20 parties en poids sec d'une partie de liant
0-6 parties en poids sec d'additifs;
et la couche de revêtement récepteur d'image comprend
100 parties en poids sec d'une partie de pigment se composant de
50 - 100 parties en poids sec d'une silice particulaire fine; et
0 - 50 parties en poids sec d'un polymère particulaire fin, comme un pigment en plastique
et/ou biopolymère,; et
0 - 30 parties de pigments particulaires fins supplémentaires
2 - 10 parties en poids sec d'un liant
0-3 parties en poids sec d'additifs.
7. Papier à jet d'encre selon la revendication 6, dans laquelle la couche de pré-revêtement
comprend 100 parties en poids sec d'une partie de pigment se composant de
40-75 parties en poids sec, préférablement 50-60 parties en poids sec, d'un carbonate
de calcium fin particulaire, moulu ou précipité;
25-70 parties en poids sec, préférablement 40-60 parties en poids sec d'un pigment
de silice fin
particulaire et/ou d'un carbonate de calcium of a particulaire fin moulu avec modification
de surface et structure interne résultante d'un traitement avec un ou plusieurs fournisseurs
moyens à forts de ions H3O+ et optionnellement avec un traitement supplémentaire au
dioxyde de carbone gazeux,
dans lequel préférablement le pigment de silice particulaire fin dans la couche de
pré-revêtement est composé de 5 - 50, préférablement 10-50 parties en poids sec d'une
silice colloïdale et 10-40 parties en poids sec d'un gel de silice,
et dans lequel plus préférablement le pigment de silice particulaire fin dans la couche
de pré-revêtement est composé de 10 - 30, préférablement 15-30 parties en poids sec
d'une silice colloïdale et 20-35, préférablement 25-35 parties en poids sec d'un gel
de silice,
et dans lequel même plus préférablement le gel de silice dans la couche de pré-revêtement
a une distribution de taille de particules de manière à ce que la taille moyenne de
particule est dans le domaine de 0.1-10 um, préférablement en dessous de 7 um et plus
préférablement en dessous de 4.0 um et/ou la silice colloïdale dans la couche de pré-revêtement
a une distribution de taille de particules de manière à ce que la taille moyenne de
particule est dans le domaine de 10 - 120 nm, préférablement 40 - 100 nm.
8. Papier à jet d'encre selon l'une quelconque des revendications 6 - 7, dans lequel
la partie de liant dans la couche de pré-revêtement comprend un liant latex et un
deuxième liant choisi du groupe de liants polyvinyle-pyrrolidone, PVA, gelatine et
mélanges de ceux-ci, dans lequel plus préférablement la partie de liant comprend 2-20,
préférablement 2-14 parties en poids sec d'un liant latex, préférablement un liant
styrène-butadiène et 2-8, préférablement 4-8 parties en poids sec d'un liant polyvinyle-pyrrolidone,
préférablement de polyvinyle-pyrrolidone avec un poids moléculaire de plus de 20'000
Da, même plus préférablement de plus de 30'000 Da, plus préférablement dans le domaine
de 40'000 Da - 80'000 Da.
9. Papier à jet d'encre selon l'une quelconque des revendications 6-8, dans lequel la
couche de pré-revêtement comprend 100 parties en poids sec d'une partie de pigment
se composant de
50-75 parties en poids sec, préférablement 40-60 parties en poids sec, d'un carbonate
de calcium fin
Particulaire, moulu ou précipité, dans lequel le carbonate de calcium particulaire
fin a une distribution de taille de particules de manière à ce que 50 % des particules
sont inférieures à 1 um, préférablement inférieures à 0.7 um;
25-50 parties en poids sec, préférablement 40-60 parties en poids sec d'un pigment
de silice fin
particulier et/ou d'un carbonate de calcium particulaire fin moulu avec modification
de surface et structure interne résultante d'un traitement avec un ou plusieurs fournisseurs
moyens à forts de ions H3O+ et optionnellement avec un traitement supplémentaire au
dioxyde de carbone gazeux.
10. Papier à jet d'encre selon l'une quelconque des revendications 6 - 9, dans lequel
la couche de revêtement récepteur d'image comprend
100 parties en poids sec d'une partie de pigment se composant de
60 - 100, préférablement 60 - 90 parties en poids sec d'un pigment de silice particulaire
fine colloïdale ; et
0 - 40, préférablement 10 - 40 parties en poids sec, préférablement 10-30 parties
en poids sec, d'un pigment polymère particulaire fin;
3 - 6 parties en poids sec d'un liant
0-2 parties en poids sec d'additifs.
11. Papier à jet d'encre selon la revendication 10, dans lequel le pigment polymère particulaire,
préférablement solide ou vacuolé dans la couche de revêtement récepteur d'image a
une distribution de taille de particules de manière à ce que plus de 90 % des particules
sont inférieures à 0.5 um, préférablement avec une distribution de taille de particules
de manière à ce que 90 % of the particules ont des tailles entre 0.05 et 0.3 um, en
particulier entre 0.1 et 0.2 um, ou dans le cas d'un pigment polymère vacuolé aussi
avec taille de particules moyenne d'environ 0.6 -1 um.
12. Papier à jet d'encre selon l'une quelconque des revendications 6 - 11, dans lequel
la partie de liant dans la couche de revêtement récepteur d'image se compose d'un
liant PVA, d'un liant PVP, d'un liant gélatine ou de mélanges de ceux-ci
et/ou dans lequel la couche de revêtement récepteur d'image comprend un mordant pour
colorants, préférablement 0.1-1.5, préférablement 0.5 - 1.5 parties en poids sec de
celui-ci
et/ou dans lequel le revêtement récepteur d'image est directement adjacent à la couche
de pré-revêtement
et/ou dans lequel la couche de pré-revêtement a une épaisseur de couche dans le domaine
de 5-30 g/m2, préférablement dans le domaine de 10-20 g/m2, et dans lequel la couche de revêtement supérieur a une épaisseur de couche dans
le domaine de 2-20 g/m2, préférablement de 5-10 g/m2
et/ou dans lequel la formulation de pré-revêtement est essentiellement libre de composantes
cationiques
et/ou dans lequel la charge du revêtement est généralement anionique
et/ou dans lequel le revêtement récepteur d'image est transparent
et/ou dans lequel les additifs dans le pré-revêtement et/ou le revêtement récepteur
d'image sont choisis du groupe de antimoussants, colorants, azurants, dispersants,
épaississants, agents de rétention d'eau, conservateurs, agent de réticulation, lubrifiants
et agents de contrôle de pH agents et mélanges de ceux-ci,
et/ou dans lequel la couche de revêtement récepteur d'image comprend un mordant pour
colorants cationique comme additif dans une quantité de 0.1-1.5 parties par poids
sec, préférablement 0.5-1 parties par poids sec
et/ou dans lequel la couche de pré-revêtement est essentiellement libre d'additifs
mordants cationiques.
13. Papier à jet d'encre selon l'une quelconque des revendications 6-12, dans lequel le
pigment de silice colloïdale dans la couche de revêtement récepteur d'image est une
silice non-modifiée anionique colloïdale
et/ou dans lequel le pigment de carbonate de calcium particulaire fin dans le pré-revêtement
est un pigment carbonate de calcium précipité, préférablement du type en forme d'aiguille
et/ou du type anionique.
14. Papier à jet d'encre selon l'une quelconque des revendications 6 - 13, dans laquelle
le papier de fin a un brillance au-delà de, ou égale à, 45% selon 75° DIN, préférablement
au-delà de, ou égale à, 50%, même plus préférablement au-delà de, ou égale à, 55%.
15. Papier à jet d'encre selon l'une quelconque des revendications 6 - 14, dans laquelle
le pré-revêtement et/ou la(les) couche(s) de revêtement récepteur sont généralement
anionique(s).