Europaisches Patentamt

European Patent Office

© Publication number: 0 561 828 B1
Office europeen des brevets

© EUROPEAN PATENT SPECIFICATION

© Date of publication of patent specification: 22.02.95 © Int. CI.6: D21 H 21/00, //D21 H1 1/00,
D21H1 7/1 4,D21H1 7 / 6 3 ,
© Application number: 91920617.7 Q21 H1 7/74, D21 H1 9 / 4 4

@ Date of filing: 25.11.91

© International application number:

PCT/SE91/00798

© International publication number:

WO 92/09745 (11.06.92 92/13)

© PAPER AND A METHOD OF PAPER MANUFACTURE.

© Priority: 03.12.90 SE 9003830 Qj) Proprietor: MO OCH DOMSJO AKTIEBOLAG

@ Date of publication of application: S-891 80 Ornskoldsvik (SE)

29.09.93 Bulletin 93/39
@ Inventor: AGNEMO, Arne, Roland
© Publication of the grant of the patent: Smed Anders vag 18
22.02.95 Bulletin 95/08 S-892 42 Domsjo (SE)

© Designated Contracting States:

AT BE CH DE DK ES FR GB IT LI NL © Representative: Weinhold, Peter, Dr. et al
Patentanwalte Dipl.-lng. G. Dannenberg
© References cited: Dr. P. Weinhold
US-A- 3 393 122 Dr. D. Gudel
US-A- 4 871 423 Dipl.-lng. S. Schubert
Dr. P. Barz
Dialog Information Services, PAPERCHEM, Siegfriedstrasse 8
Dialog Accession no. 500658, Fornier de Vio- D-80803 Munchen (DE)
let, P et al; "Photochemical Brightness Re-
version of Peroxide-Bleached Mechanical
Pulps in the Presence of Various Additives",
00 Cellul, Chem. Technol.24, no. 2:225-235
(March/April 1990)
00
CM
00

CO
Note: Within nine months from the publication of the mention of the grant of the European patent, any person
may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition
shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee
has been paid (Art. 99(1) European patent convention).
Rank Xerox (UK) Business Services
(3. 10/3.09/3.3.3)
 EP 0 561 828 B1

Description

Tecnical field

5 The invention relates to paper which, with regard to the fibre part, is based on material which at least
consists partially of lignin-containing pulp. Examples of this type of pulp are so-called high yield pulps, such
as groundwood pulps (conventional and pressure), thermomechanical pulps and chemi-thermomechanical
pulps. These and other pulps mentioned in this specification are, in turn, produced from any kind of
lignocellulosic material whatsoever, including wood. The invention relates primarily to paper of the newsprint
io kind (conventional and so-called improved), wood-containing printing and writing paper, for instance
magazine paper, such as super calandered (SC) paper, low weight coated (LWC) paper, medium weight
coated (MWC) paper, white liner and fine paper, both coated and uncoated. As used in the present
specification, the term paper also includes different types of paperboard.
The invention also relates to a method for producing the aforedescribed papers.
75
Background art

In present-day processes and also in past manufacturing processes, the fibre part of the aforesaid
papers comprises/comprised varying quantities of lignin-containing pulp. The remaining fibre quantity
20 normally consists of lignin-free pulp, such as bleached chemical pulp. Lignin-containing pulps, for example
high yield pulps, provide several advantages when used as paper ingredients. One advantage is that this
type of pulp, even when bleached, is cheaper than chemical pulps in general, and particularly bleached
chemical pulps. Another advantage is that several properties of the paper can be improved when the fibre
part of the paper includes a given quantity of high yield pulp, as compared with paper which is based solely
25 on chemical pulp. Examples of such properties are opacity (non-transparency), stiffness and bulk.
The big drawback with mixing high yield pulps in paper is that the paper becomes pronouncedly
discoloured (yellows) with time. All pulps, and consequently all paper that is based on pulps, will yellow with
time. A bleached chemical pulp which contains solely carbohydrates and no lignin at all will also yellow to a
certain extent. The extent to which these pulps yellow, however, cannot be compared with the yellowing of
30 pulps that contain lignin. In the case of this latter pulp, yellowing is dominated by the lignin and is
accelerated by contact of the fibres with light. This accelerated yellowing of the pulps is caused particularly
by the shortwave part of the light, i.e. that part of the light which has a wavelength beneath 425 nm. This
drawback of high yield pulps has delayed the use of such pulps in general and/or has at least limited the
percentage admixture of such pulps in the fibre part of paper of the aforedescribed type.
35 Several proposals have been made with regard to limiting the yellowing (improving the brightness
stability) of paper which is based completely or partially on lignin-containing pulp.
One method is to reduce the amount of shortwave light, which penetrates the paper. This can be
achieved, for instance, by adding to the paper a pigment which has a pronounced ability of spreading
shortwave light, as taught in the article "Ny metod mot gulnande papper" by Kenneth Leverback, Kemisk
40 Tidskrift 1990, No. 10. pages 38-39, or by introducing into the paper chemicals which will convert ultraviolet
light to heat. This latter type of chemical is normally an organic substance having a phenolic structure.
According to US-A-4 871 423 various compounds including ascorbic acid, palmitoyl ascorbate and
sodium dithionite were tested as pulp brightness enhancement agents of which only the two former
compounds were effective.
45 Another method of limiting the yellowing of lignin-containing pulp and of paper produced therefrom is
described in EP-A- 0 280 332). There is told that bleached lignin-containing pulp is reacted with a reduction
agent, for example, and preferably, sodium borhydride, in an after treatment process carried out already in
the pulp mill. According to the simplest embodiment of the claimed method, a fluroescent chemical, for
example an optical whitener, is then introduced to the pulp. This procedure can either be carrid out directly
50 on the pulp in the pulp mill or in the paper mill to paper produced from the pulp, for example when surface
sizing or surface coating the paper.

Disclosure of the invention

55 Technical problems

Although the aforedescribed methods, and particularly the latter method, will appreciably limit the extent
to which paper comprised at least partially of lignin-containing pulp will yellow, there is a need of alternative

2
 EP 0 561 828 B1

solutions which are effective both from a functional aspect and from the aspect of cost.

Solution

5 The present invention provides one such solution and relates to paper produced from fibre material
which comprises at least partially pulp which contains lignin in an amount exceeding 0.5 percent by weight,
and which comprises at least one chemical, including retention agent and/or hydrophobizing agent and/or
dry strength agent, and is characterized in that the paper includes
a) an acid and/or corresponding salt of the general formula (the acid form)
10
OH OH

C C
15

where
Ri = -CHOHCH2OH or - CHOHCOOH
25 in a quantity of at least 0.05 percent by weight, calculated on the fibre material; and
b) a reduction agent in an amount of at least 0.05 percent by weight, calculated on the fibre material.
Suitable additives according to a) are ascorbic acid, arabo-ascorbic acid, saccharo ascorbic acid and
xyloascorbic acid and/or their salts.
Ascorbic acid has been found very suitable in the present context, and particularly the L-form of the
30 acid and/or its salt. The L-form is to be preferred also with regard to the remaining acids and/or their salts,
with the exception of xylo-ascorbic acid and/or its salt, where the D-form is to be preferred.
The reduction agent according to b) may be any kind of reduction agent whatsoever, such as boron
hydride, dithionite, hydrazine, thiourea-dioxide and hydrogen sulphite/sulphite. Catalytic hydration can also
be used. The reduction agents preferred are those which are both effective and which command a low
35 price. Additives which include hydrogen sulphite and/or sulphite are particularly preferred.
As suitable fibre mixture and admixture of additives of the two aforedescribed types will result in a
paper whose initial brightness exceeds 70% ISO, measured according to SCAN-C 11:75. In general, all
brightness values recited in this specification, i.e. with regard to the different pulps and also to the different
papers, are measured in accordance with this method. Another characteristic of the paper is that it has good
40 brightness stability, meaning that the light absorption coefficient of the paper is beneath 1.50 m2/kg
measured according to SCAN-C 11:75, subsequent to irradiating the paper with a Landau zenon lamp for
two hours.
The additives according to a) and b) above may advantageously be uniformly distributed within the
paper, i.e. also seen in the cross-section area of the paper. It is preferred, however, to concentrate the
45 agents at the surface of the paper, i.e. one or both surface parts thereof.
The scope of the present invention includes several sorts of paper, i.e. both existing types of paper and
future types. Examples of present-day, common paper types according to the invention and their construc-
tion are disclosed in the following.
70-100% of the fibre part of newsprint consists of mechanical pulp, i.e. unbleached groundwood pulp or
50 unbleached thermomechanical pulp, and 30-0% of chemical pulp. The paper may contain small quantities
of pigment. Examples of pigment are calcinated clay, aluminium hydroxide, silicates and organic com-
pounds. These pigments may be introduced either individually or in mixture. The paper will normally also
include a retention agent, for example of the kind polyacrylamide, polyethylene imine or a multi-component
system consisting, for instance, of polyethylene oxide and phenol resin. Nuancing dyes are sometimes
55 added. The surface weight of newsprint normally lies within the range of 40-50 g/m2.
So-called improved newsprint normally includes bleached mechanical pulp, and may also contain small
quantities of pigment and other additives, according to the above. Improved newsprint normally has a
surface weight within the range of 50-70 g/m2.

3
 EP 0 561 828 B1

Examples of coated wood-containing paper are low weight coated (LWC) paper and medium weight
coated (MWC) paper. The fibre composition of these papers can vary from 100% high yield pulp to a
mixture of 50% high yield pulp and 50% chemical pulp. The surface weight of respective papers with
regard to the fibre part is 35-45 g/m2 and 45-75 g/m2. The paper will normally include a retention agent and
5 5-10% mineralic pigment in the base paper, calculated on the dry paper. This paper is coated on both sides
thereof with a coating agent (layers) in an amount of 5-20 g, calculated on dry weight per m2. The coating
agent is applied to the paper in the form of a paste which contains one or more of the substances taken
from the following group; various kinds of pigment, for example clay and calcium carbonate, binder, such as
latex, and starch, wet strength resin, carboxymethyl cellulose, nuancing dyes, etc.
io Another type of paper is supercalandered (SC) paper, which normally has a surface weight of 50-80
g/m2. The fibre part consists of a mixture of mechanical pulp and chemical pulp, for instance in the ratio of
70:30. The paper has a high filler content, about 20-30% calculated on the dry paper. The paper also
contains retention agents in an amount, for instance, of 0-0.5%, calculated on the dry fibre content. The
paper may also contain, at times, a hydrophobizing agent, such as alum and resin acid, in an amount of, for
is instance, 0-2%, calculated on the dry fibre content, an a low amount of nuancing dyes.
Another type of paper is fine paper. The surface weight of fine paper lies within the range of 40-140
g/m2. The fibre part is made predominantly of chemical pulp, which normally constitutes 90-100% of the
fibre part. The remaining fibre content, i.e. up to 10%, may consist of high yield pulp. The paper normally
includes 5-30% filler, calculated on the dry paper, and a number of additives, such as hydrophobizing agent
20 (0-1%), retention agent (0-0.5%), dry strength agent (for instance cationic starch in an amount of 0-4%),
optical whiteners (0-2%) and a small quantity of nuancing dyes. Examples of fillers are clay, chalk, calcite,
marble, talc and titanium dioxide. The next outermost layer, or the outermost layer of the paper, normally
consists of a surface sizing layer, for instance in the form of some kind of starch. The amount used is 0-5
g/m2 (calculated as dry weight). Alternatively, the outermost layer consists of a coating layer applied in an
25 amount of 0-30 g/m2 and side (calculated as dry weight). It will be understood from this that fine paper may
be either uncoated or coated. The invention enables the high yield pulp proportion in fine paper to be
increased to above 50%.
By paperboard is meant a paper product having a high surface weight, for instance a surface weight of
120-400 g/m2, and which normally comprises several layers. Paperboard may contain both chemical pulp
30 and high yield pulp. The mixture of these pulps varies markedly from manufacturer to manufacturer.
Paperboard normally includes hydrophobizing agents and dry strength agents, but to a lesser extent fillers
and retention agents.
A common feature of all paper according to the invention, including the aforedescribed papers, is that at
least a part of the fibre material from which the paper is constructed consists of lignin-containing pulp,
35 preferably high yield pulp. A preferred and essential feature of the invention is that this pulp is bleached in
one or more stages. Such pulp is normally bleached with peroxide, although pulps which have been
bleached with other bleaching agents, such as boron hydride and dithionite, for instance, are well-suited as
an ingredient of the inventive paper.
Because the paper contains the additives a) and b) the paper manufacturer can be more selective with
40 regard to the choice of pulp mixture.
Hitherto, reference has been made solely to different types of pulps as the source of fibre material.
Naturally, the paper may also include a given proportion of other fibres, such as return fibres and
regenerated fibres of different kinds, and also synthetic fibres.
The invention also relates to a method for manufacturing paper that contains fibre material which at
45 least partially consists of pulp which contains lignin in an amount exceeding 0.5 percent by weight and at
least one chemical, including retention agent and/or hydrophobizing agent and/or dry strength agent,
characterized in that there is introduced to the paper at any position whatsoever after forming the paper

50

55

4
 EP 0 561 828 B1

a) an acid and/or corresponding salt of the general formula (acid form)

OH OH

5
c c

0 c ,CH - R
w

is where Ri = -CHOHCH2OH or - CHOHCOOH

in an amount of at least 0.05 percent by weight, calculated on the fibre material; and
b) a reduction agent in an amount of at least 0.05 percent by weight, calculated on the fibre material.
The paper is formed from a stock, an aqueous suspension, which in addition to the earlier described
fibre mixture also includes one or more of the earlier mentioned paper ingredients, such as retention agent,
20 filler, pigment, hydrophobizing agent, nuancing dyes, etc. The pH of the stock lies within the range of 4-10.
Subsequent to having passed through the headbox of the paper machine, the stock is fed onto a liquid-
permeable wire, which is advanced at a given speed. As the wire advances, the stock is dewatered
successively and the actual paper is formed. The fibre concentration of the stock is normally between 0.1-
2%, and when forming of the paper is essentially complete, its dry solids content is about 3-7%. This dry
25 solids content varies from case to case, i.e. in the so-called dry line of a paper machine.
Subsequent to forming the paper, both the additive a) and the additive b) according to the above are
applied to the paper, preferably in the form of aqueous solutions. Examples of both suitable and preferred
additives according to a) and b) have been earlier described. The additives concerned can either be applied
to the paper separately or together.
30 Distribution of the additives in the cross-section of the paper is determined by the positioned at which
the addition is made in the forward direction of movement of the paper and on the dry solids content of the
paper at the time of making the addition.
A paper machine normally includes a press section and the additives can be delivered to the paper
immediately upstream of, in or immediately downstream of the press section. When the paper is of a kind
35 which is surfaced sized, the two additives may advantageously be delivered to the paper either when sizing
the paper or in connection therewith. If the paper is coated, the two additives may advantageously be
delivered to the paper when coating the paper or in connection therewith. The occasions represented by the
words when and in connection with are equivalent additive supply positions or occasions. Naturally, the two
additives can be delivered to the paper in several positions.
40 In those cases when both additives are supplied to the paper at the time of sizing or coating the paper,
the additives may well be added in solid form (powder) to the sizing suspension and the coating paste
respectively. On both of these occasions, and also when dissolving the additives concerned in solely water,
the ascorbic acid addition will result in a pH which is considerably below 7. It is possible to adjust the pH of
the solution to, e.g. the range of 6-9, with the aid of an alkali. By alkali is meant, for instance, sodium
45 hydroxide, sodium carbonate, potassium hydroxide and ammonia. This means that the majority, and often a
totally predominant part of the ascorbic acid present in the paper will have converted to a corresponding
simple salt. Ascorbic acid has two pKa-values, namely pKai = 4.2 and pKa2 = 11.6. As a result, the
ascorbic acid will release a hydrogen atom (proton) within the pH-range of 6-9, this atom being replaced, for
instance, with a sodium atom. Naturally, the alkali may be based on a cation other than sodium and in such
50 case, it is this ion which will replace the hydrogen ion. The preferred addition of respective chemicals lies
within the range of 0.25-2 percent by weight, calculated on the fibre material.
Irrespective of the position in which the two additives are introduced to the paper, the paper is
subsequently dried on drying cylinders in at least one step, at a highest cylinder temperature which
exceeds 100°C. Highest cylinder temperatures up to 130°C are normal.
55

5
 EP 0 561 828 B1

Advantages

The yellowing of paper manufactured in accordance with the invention is so reduced as to approach the
yellowing of paper that has been manufactured exclusively from bleached chemical pulp. As a result of the
5 invention, it is possible to increase in the paper the quantity of fibres from lignin-containing pulps at the cost
of the fibre quantity from lignin-free chemical pulps at a substantially unchanged quality and with regard to
certain properties an improved result. This enables the manufacturing costs of the paper to be reduced, at
least with some sorts of paper. This cost reduction is obtained for at least two reasons, firstly part of the
expensive chemical pulp can be exchanged for a cheap high yield pulp, and secondly the surface weight of
io the paper can be reduced, leading to reduced fibre usage. Furthermore, the paper manufacturer has a
greater degree of freedom in selecting the fibre composition of a given paper. As a result of the invention,
those types of paper which already have a high proportion of fibres deriving from lignin-containing pulps
have a markedly improved quality.

is Best mode of carrying out the invention

Down below are shown a number of Examples in which paper in accordance with the invention was
constructed on a small, laboratory scale, and with which the inventive method has been simulated.

20 Example 1

Two types of paper, one paper type for application of the invention and one wood free reference paper,
were produced on a laboratory paper machine having a web width of 22 cm.
In the case of the first mentioned type of paper, 50 parts of bleached aspen groundwood pulp having a
25 brightness of 84.9% ISO were mixed in a vessel, in water, with 50 parts of bleached softwood sulphate pulp
having a brightness of 85.3% ISO, this pulp previously having been refined to a refining degree of 25 SR
(Schopper-Riegler), such as to obtain a fibre suspension having a dry solids content pronouncedly beneath
1%. Filler in the form of marble sold under the trade name Hydrocarb 65 was added to another vessel
which contained water, such as to obtain a solids content of 4%. These two suspensions were mixed in the
30 ratio of 80 to 20, based on solids content in respective cases, so as to form a stock. As dry strength agent,
there was added 0.8% cationic potatoe starch sold under the trade name Q-tac 300 B5, and a ketene dimer
sold under the trade name Aquapel 239 was added as a hydrophobizing agent in a quantity of 3% (as a
commercial product), calculated on the dry weight of the paper. Also added was a retention agent in the
form of polyacrylamide sold under the trade name PAM HY 1141 in an amount of 0.008%, calculated on the
35 dry weight of the paper, and Bentonit type clay having the designation HWE in a quantity of 0.05%,
calculated on the dry weight of the paper. The pH of the stock was finally adjusted to 8.0, with the aid of
sodium hydrogencarbonate.
When pumped into the headbox of the paper machine, the stock has a solids content of 0.2%.
Subsequent to forming the paper on the wire section of the paper machine, the paper was introduced into a
40 press section, whereafter the paper was dried with the aid of electrically heated cylinders at a highest
cylinder temperature of 130°C. The paper machine terminated with paper sizing equipment with which the
paper was sized with a starch sold under the trade name Perfect Amyl in an amount of 1.20 grams of
absolutely dry starch per m2 of paper. The starch was applied to the paper in the form of a 10%-solution.
Prior hereto, powdered L-ascorbic acid and powdered sodium sulphite were added to the starch solution.
45 This caused the pH of the suspension to fall significantly, and sodium hydroxide was therefore added to
obtain a pH of 7.0. At a pH of 7.0, both hydrogen sulphite ions (HSO3 ) and sulphite ions (SO§~ ) exist in a
50/50 distribution. The paper had a dry solids content of 98% prior to the sizing process, the dry solids
content fell to 75% and the paper was then dried with electrically heated cylinders at a highest cylinder
temperature of 110°C, to a dry solids content of 96%. The finished paper had a surface weight of 60 g/m2.
50 The tests hitherto described are concerned with the manufacture of paper in accordance with the
invention. Further tests were carried out with a similar base paper for comparison purposes. In one of these
tests, neither ascorbic acid nor sodium sulphite were added to the starch suspension. Further, only ascorbic
acid was added to the starch suspension, in three different quantities, and solely sodium sulphite was
added, in two different quantities.
55 A reference paper was also produced. This paper was produced in the manner already described. The
difference lied solely in the fibre composition. The fifty parts of bleached aspen groundwood pulp were
replaced with fifty parts of bleached birch sulphate pulp, which was refined to 20 SR. This pulp has a
brightness of 85.8% ISO. The reference paper thus contained totally, i.e. to 100% fibres that derived from

6
 EP 0 561 828 B1

bleached chemical pulp, so-called wood free paper. The two chemicals characteristic of the present
invention were not added to this paper.
The aforedescribed papers were obtained in the form of a roll at the end of the paper machine.
Samples were taken from each roll and initial values relating to brightness and light absorption coefficient
5 were measured. Further samples were taken and these samples were subjected to light aging and to heat
aging, whereafter brightness and light absorption coefficient were determined. Light aging was determined
by illuminating the papers with a Landau-type xenon lamp for different periods of time, while heat aging was
determined by placing the paper in a heated cabinet for 16 hours at a temperature of 120°C.
The amount of ascorbic acid and sodium sulphite added and the results achieved are disclosed in
io Table 1 below.

7
 EP 0 561 828 B1

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As will be seen from the results disclosed above, where solely the tests 7 and 8 are in accordance with
the invention, the two papers 7 and 8 initially exhibit, i.e. immediately after producing the paper, the same
brightness values and the same light absorption coefficients as the paper 1, i.e. the starting paper to which
neither ascorbic acid nor sodium sulphite were added. The two aging tests show, however, that the
brightness stability of the two papers according to the invention is superior to the brightness stability of the

8
 EP 0 561 828 B1

starting paper. Subsequent to being irradiated over a period of, e.g., 9 hours with an xenon lamp (simulating
day/sunlight radiation) the paper 1 had a brightness of 75.9% ISO and a light absorption coefficient of 2.64,
whereas the paper 7 according to the invention exhibited a brightness of 81 .3% ISO and a light absorption
coefficient of 1.53. During the heat aging test, the brightness of the paper 1 fell to 79.9% ISO, whereas the
5 brightness of the paper 7 fell to only 82.2% ISO.
The tests 2-4, which relate to the addition of solely ascorbic acid to the paper, and in increasing
quantities, surprisingly shows, that the initial brightness of the paper fell as a result of the ascorbic acid
addition, and that the reduction in brightness increases with increasing addition quantities. The initial
brightness of 85.5% ISO of the starting paper fell to 81.3% ISO when adding 2.1% ascorbic acid, calculated
io on the dry paper weight. With regard to light aging, however, the addition of ascorbic acid results in a
slightly improved brightness stability compared with the starting paper. With regard to heat aging, the result
of the ascorbic acid addition is catastrophically poor. Ascorbic acid is thus not heat stable. The reduction in
the initial brightness of the paper when adding ascorbic acid is probably because when drying the paper,
the paper is subjected to a highest cylinder temperature which exceeds 100°C and reaches towards
15 130 °C.
When adding solely sodium sulphite to the paper, the tests 5 and 6, the initial brightness is generally
the same, or possibly somewhat improved in comparison with the starting paper. However, the addition of
sodium sulphite had no brightness stabilizing effect with regard to light aging, whereas a certain improve-
ment was obtained in comparison with the starting paper with regard to heat aging.
20 Surprisingly good results with regard to brightness stability were thus obtained with the inventive paper,
i.e. the tests 7 and 8. When making a comparison between the inventive papers, for instance the paper 7
and the paper 9, which is a wood free reference paper, i.e. the fibre part of which was produced exclusively
from bleached chemical pulp, it will be seen that the initial brightness of the reference paper 9 is about 3
units higher than the brightness of the inventive paper and that the initial light absorption coefficient of the
25 reference paper 9 is only slightly more than half of the light absorption coefficient of the inventive paper.
Subsequent to light aging the two papers for 9 hours, the difference in brightness was reduced to 0.8 units
and the difference in light absorption coefficient was also significantly reduced.

Example 2
30
Four further papers were produced in the aforedescribed manner.
The only difference between this test series and the test series described in Example 1 was that the 50
parts of bleached aspen groundwood pulp having a brightness of 84.9% ISO were replaced with 50 parts of
bleached spruce groundwood pulp having a brightness of 75.3% ISO. Samples of the finished papers were
35 taken and the brightness and light absorption coefficients of these papers were determined, partly initially
and partly subsequent to light aging with the aid of an xenon lamp over a period of 1, 3 and 9 hours
respectively. No heat aging tests were carried out.
The quantities in which ascorbic acid and sodium sulphite were added are disclosed in Table 2 below,
together with the results obtained.
40

45

50

55

9
 EP 0 561 828 B1

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In the above Table, only the paper 13 is in accordance with and has been produced in accordance with
the invention.
55 When solely ascorbic acid is added to the paper, the paper 11, the brightness is initially poorer than
that of the starting paper, i.e. the paper 10. This addition also results initially in am impaired light absorption
coefficient, i.e. the light absorption coefficient of the paper 11 is initially higher than that of the starting
paper 10. The additition of ascorbic acid, however, stabilizes brightness to some extent, since after being

10
 EP 0 561 828 B1

irradiated for 9 hours with an xenon lamp, the paper 11 exhibited both higher brightness and lower light
absorption coefficient in comparison with the starting paper 10 after subjecting this paper to similar
irradiation.
The sodium sulphite addition, the paper 12, results in an increased initial brightness and decreased
5 initial light absorption coefficient in comparison with the starting paper 10. This latter addition, however,
does not result in stabilization of the brightness of the paper.
A markedly better result is shown by the paper 13, manufactured in accordance with the invention, i.e.
where both ascorbic acid and sodium sulphite have been added to the paper. In comparison with the
starting paper, the inventive paper exhibits both improved initial brightness and a markedly improved
io brightness stability.

Example 3

A further five papers were produced in a test series in the manner described in Example 1.
is The only difference was that the 50 parts of bleached aspen groundwood pulp having a brightness of
84.9% ISO were replaced with 50 parts of bleached chemi-thermomechanical pulp produced from aspen
having a brightness of 85.3% ISO. Samples of the finished paper were taken and the brightness and light
absorption coefficient of the paper determined, partly initially and partly after subjecting the paper to a light
aging process with the aid of an xenon lamp over a period of 1, 2, 6 and 9 hours respectively. No heat
20 aging tests were carried out.
The amount of ascorbic acid and sodium sulphite added are disclosed in Table 3 below, together with
the results achieved.

11
 EP 0 561 828 B1

r« r» oo m
CM —
i I 10 CM
(N CN CM fH

o p» © v
f t m oo o
p» p- r» p« oo

H CN N 10 *
O O 00 «* rH
(V Ci r4 r-i

W ffi (N fl N
in m h ffi H
p» r» r* r- oo

in cm
00 V0 in o oo
H H O

CM
19 00 Ol N n
r» r- r» co oo

oo vo vo po m
CM H
iI —
— iI —
iI o ©

Is V f) H f
• • • • •
© o h m
00 00 00 00 00

iH ro ve cn
P» o m m
•Si O —iI o o o
10 00
a H
CN 10 10 10
00 00 00 00 00

o
00 m
oo' 8
o o 10 •H
+J
to

CM 00
CM *f
© CM O P* H
w
•H
«* m i0 p«- oo

In this test series, the papers 17 and 18 are produced in accordance with the invention.
The results obtained were again similar to the two test series previously reported. When making
comparisons internally between the two papers according to the invention, it was found that a marked
improvement in brightness stabilization was obtained when the quantities of the two additives were doubled.
In Example 1, on the other hand, a slightly improved brightness stability was obtained at the lower addition.

12
 EP 0 561 828 B1

This is possibly because the optimum addition quantity of these two additives is dependent on the type of
lignin-containing pulp present in the paper.

Claims

1. A paper produced from fibre material which consists at least partially of pulp that contains lignin in a
quantity which exceeds 0.5 percent by weight, and which comprises at least one chemical, including
retention agent and/or hydrophobizing agent and/or dry strength agent, characterized in that the paper
includes
a) an acid and/or corresponding salt of the general formula (the acid form)

OH OH

where
Ri = - CHOHCH2OH or - CHOHCOOH
in an amount of at least 0.05 percent by weight, calculated on the fibre material; and
b) a reduction agent in an amount of at least 0.05 percent by weight, calculated on the fibre material.

2. A paper according to Claim 1, characterized in that the acid according to a) is ascorbic acid.

3. A paper according to Claims 1-2, characterized in that the reduction agent according to b) is a
substance that contains hydrogen sulphite and/or sulphite.

4. A paper according to Claims 1-3, characterized in that its initial brightness exceeds 70% ISO,
measured according to SCAN-C 11:75.

5. A paper according to Claims 1-4, characterized in that its brightness stability is such that it has a
brightness absorption coefficient of beneath 1.50 measured in m2/kg according to SCAN-C 11:75 after
being irradiated with an xenon lamp for two hours.

6. A paper according to Claims 1-5, characterized in that the additives according to a) and b) are
concentrated to the surface of the paper.

7. A method for manufacturing paper comprising fibre material, which at least partially consists of pulp
containing lignin in an amount exceeding 0.5 percent by weight, and at least one chemical, including
retention agent and/or hydrophobizing agent and/or dry strength agent, characterized in that there is
introduced to the paper in any position whatsoever after forming said paper

13
 EP 0 561 828 B1

a) an acid and/or corresponding salt of the general formula (the acid form)

OH OH

CH"
10

w where Ri = - CHOHCH2OH or - CHOHCOOH

in an amount of at least 0.05 percent by weight, calculated on the fibre material; and
b) a reduction agent in an amount of at least 0.05 percent by weight, calculated on the fibre material.

8. A method according to Claim 7, characterized in that the stock from which the paper is formed has a
20 pH of 4-10.

9. A method according to Claims 7-8, characterized in that the additive according to a) is ascorbic acid.

10. A method according to Claims 7-9, characterized in that the additive according to b) is a substance
25 that contains hydrogen sulphite and/or sulphite.

11. A method according to Claims 7-10, characterized in that the additives a) and b) are introduced to the
paper in conjunction with pressing the paper during its manufacture.

30 12. A method according to Claims 7-10, characterized in that the additives a) and b) are introduced to the
paper when surface sizing said paper.

13. A method according to Claims 7-10, characterized in that the additives a) and b) are introduced to the
paper when coating said paper.
35
14. A method according to Claims 7-13, characterized in that subsequent to introducing said additives to
said paper, the paper is dried on drying cylinders at a highest cylinder temperature greater than
100°C.

40 Patentanspruche

1. Papier, hergestellt aus Fasermaterial, das zumindest teilweise aus Halbstoff besteht, der Lignin in einer
Menge von mehr als 0,5 Gew.-% enthalt, und welcher wenigstens eine Chemikalie einschlieBlich ein
Retentionsmittel und/oder ein Hydrophobierungsmittel und/oder ein Trockenfestigkeitsmittel umfaBt,
45 dadurch gekennzeichnet, dal3 das Papier umfaBt
a) eine Saure und/oder ein entsprechendes Salz der allgemeinen Formel (in Saureform)

OH OH

50

14
 EP 0 561 828 B1

worin
Ri = -CHOHCH2OH Oder -CHOHCOOH ist,
in einer Menge von wenigstens 0,05 Gew.-%, bezogen auf das Fasermaterial; und
b) ein Reduktionsmittel in einer Menge von wenigstens 0,05 Gew.-%, bezogen auf das Fasermateri-
5 al.

2. Papier nach Anspruch 1, dadurch gekennzeichnet, dal3 die Saure nach a) Ascorbinsaure ist.

3. Papier nach Anspruch 1 - 2, dadurch gekennzeichnet, dal3 das Reduktionsmittel nach b) eine Substanz
10 ist, die Hydrogensulfit und/oder Sulfit enthalt.

4. Papier nach Anspruch 1-3, dadurch gekennzeichnet, dal3 dessen ursprungliche Helligkeit 70% ISO,
gemessen nach SCAN-C 11:75, ubersteigt.

15 5. Papier nach Anspruch 1-4, dadurch gekennzeichnet, dal3 dessen Helligkeitsstabilitat einen Helligkeits-
Absorptionskoeffizienten unter 1,50, gemessen in m2/kg nach SCAN-C 11:75, aufweist, nachdem es 2
Stunden mit einer Xenon-Lampe bestrahlt wurde.

6. Papier nach Anspruch 1-5, dadurch gekennzeichnet, dal3 die Additive nach a) und b) an der Oberflache
20 des Papiers konzentriert sind.

7. Verfahren zur Herstellung von Papier, das Fasermaterial umfaBt, welches wenigstens teilweise aus
Halbstoff besteht, der Lignin in einer Menge von mehr als 0,5 Gew.-% und wenigstens eine Chemikalie
einschlieBlich ein Retentionsmittel und/oder Hydrophobierungsmittel und/oder Trockenfestigkeitsmittel
25 enthalt, dadurch gekennzeichnet, dal3 in das Papier in jedem beliebigen Zustand nach der Bildung des
genannten Papiers eingefuhrt wird:
a) eine Saure und/oder ein entsprechendes Salz der allgemeinen Formel (in Saureform)

OH OH

C C

35 O C CH R.

\ �

40
worin
R1 = -CHOHCH2OH Oder -CHOHCOOH ist,
in einer Menge von wenigstens 0,05 Gew.-%, bezogen auf das Fasermaterial; und
b) ein Reduktionsmittel in einer Menge von wenigstens 0,05 Gew.-%, bezogen auf das Fasermateri-
45 al.

8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dal3 der Ganzstoff, aus welchem das Papier
geformt wurde, einen pH-Wert von 4-10 aufweist.

50 9. Verfahren nach Anspruch 7-8, dadurch gekennzeichnet, dal3 das Additiv nach a) Ascorbinsaure ist.

10. Verfahren nach Anspruch 7-9, dadurch gekennzeichnet, dal3 das Additiv nach b) eine Substanz ist, die
Hydrogensulfit und/oder Sulfit enthalt.

55 11. Verfahren nach Anspruch 7-10, dadurch gekennzeichnet, dal3 die Additive a) und b) in das Papier in
Zusammenhang mit dem Satinieren des Papiers wahrend der Herstellung eingefuhrt werden.

15
 EP 0 561 828 B1

12. Verfahren nach Anspruch 7-10, dadurch gekennzeichnet, dal3 die Additive a) und b) in das Papier
eingefuhrt werden, wenn die Papieroberflache geleimt wird.

13. Verfahren nach Anspruch 7-10, dadurch gekennzeichnet, dal3 die Additive a) und b) in das Papier
5 eingefuhrt werden, wenn das Papier beschichtet wird.

14. Verfahren nach Anspruch 7-13, dadurch gekennzeichnet, dal3 nachfolgend nach der Einfuhrung der
genannten Additive in das Papier dieses auf Trockenzylindern bei hochster Zylindertemperatur von
mehr als 100° C getrocknet wird.
10
Revendicatlons

1. Papier produit a partir d'une matiere fibreuse composee, au moins partiellement, de pate contenant de
la lignine en quantite excedant 0,5 pour cent en poids et composee d'au moins une substance
is chimique, incluant un agent de retention et/ou un agent hydrophobisant et/ou un agent de stabilite a
sec, ce papier etant caracterise par le fait qu'il incorpore:
a) un acide et/ou un sel correspondant de formule generale (pour la forme acide)

20

25 CH— Ri

30
ou Ri = - CHOHCH2OH ou - CHOHCOOH
en quantite egale au moins a 0,05 pour cent en poids, calculee sur la matiere fibreuse; et
b) un agent reducteur en quantite egale au moins a 0,05 en poids, calculee sur la matiere fibreuse.

35 Papier selon la revendication 1, caracterise par le fait que I'acide selon a) est I'acide ascorbique.

Papier selon I'une ou I'autre des revendications 1 ou 2, caracterise par le fait que I'agent reducteur
selon b) est une substance contenant de I'hydrosulfite et/ou du sulfite.

40 4. Papier selon I'une quelconque des revendications 1 a 3, caracterise par le fait que son degre de
blancheur initial depasse 70% ISO, mesure selon SCAN-C 11:75.

Papier selon I'une quelconque des revendications 1 a 4, caracterise par le fait que la stabilite de la
blancheur est telle que son coefficient d'absorption de lumiere, mesure selon SCAN-C 11:75, se situe
45 au-dessous de 1,50 m2/kg apres irradiation avec une lampe au xenon pendant deux heures.

Papier selon I'une quelconque des revendications 1 a 5, caracterise par le fait que les additifs selon a)
et b) sont concentres a la surface du papier.

50 Procede pour la fabrication de papier contenant une matiere fibreuse composee, au moins partielle-
ment, d'une pate contenant de la lignine en quantite superieure a 0,5 pour cent en poids et d'au moins
une substance chimique incluant un agent de retention et/ou un agent hydrophobisant et/ou un agent
de stabilite a sec, ce procede etant caracterise par le fait que Ton ajoute au papier, a toute position
quelle qu'elle soit, consecutive a sa formation,
55

16
 EP 0 561 828 B1

a) un acide et/ou le sel correspondant de formule generale (pour la forme acide)

OH OH
5 | |

0 = C CH - Ri
w

O'

w ou Ri = - CHOHCH2OH ou - CHOHCOOH
en quantite egale au moins a 0,05 pour cent en poids, calculee sur la matiere fibreuse; et
b) un agent reducteur en quantite au moins egale a 0,05 en poids, calculee sur la matiere fibreuse.

8. Procede selon la revendication 7, caracterise par le fait que la pate de papier a partir de laquelle le
20 papier est forme a un pH compris entre 4 et 10.

9. Procede selon I'une ou I'autre des revendications 7 ou 8, caracterise par le fait que I'additif selon a) est
de I'acide ascorbique.

25 10. Procede selon I'une quelconque des revendications 7 a 9, caracterise par le fait que I'additif selon b)
est une substance contenant de I'hydrosulfite et/ou du sulfite.

11. Procede selon I'une quelconque des revendications 7 a 10, caracterise par le fait que les additifs a) et
b) sont ajoutes au papier en liaison avec son passage aux presses au cours de sa fabrication.
30
12. Procede selon I'une quelconque des revendications 7 a 10, caracterise par le fait que les additifs a) et
b) sont ajoutes au papier au moment du collage superficiel de celui-ci.

13. Procede selon I'une quelconque des revendications 7 a 10, caracterise par le fait que les additifs a) et
35 b) sont ajoutes au papier au moment du couchage superficiel de celui-ci.

14. Procede selon I'une quelconque des revendications 7 a 13, caracterise par le fait que, consecutivement
a I'addition des additifs au papier, celui-ci est seche sur des cylindres secheurs, a une temperature
maximale des cylindres excedant 100°C.
40

45

50

55

17