Note: Descriptions are shown in the official language in which they were submitted.
~08~7g~
SPECIFICATION
[Title of the Invention]
Rosin emulsion composition for paper sizing and
method of sizing using the same
[Field of the Invention]
This invention relates to a rosin emulsion sizing
agent for papermaking and a sizing method using the same.
More specifically, it is concerned with a rosin emulsion
composition for paper sizing obtained by emulsifying and
dispersing a rosinous substance containing a specific
amount of at least one fortified or unfortified compound
of an ester formed from a rosin and at least one of a
polyhydric alcohol having not less than three hydroxyl
groups per molecule, a polyhydric phenol and a mixture of
alcohol and/or phenol mainly comprising polyhydric alco-
hol and/or phenol as defined above directly in water with
the aid of a cationic acrylamide polymer and/or methacryl-
amide polymer (hereinafter referred to as cationic
(meth)acrylamide polymer) having a hydrophobic group,
which is excellent in mechanical and storage stabilities
in itself and exhibits an excellent sizing effect in
papermaking systems of acidic to neutral pH ranges and
remarkably reduces foaming which is caused when a sizing
agent is used in the papermaking system, and a sizing
method using the same.
Development of measures to meet the improvement of
paper quality and the employment of the closed water
recycling system is an issue of urgent necessity in the
papermaking industry. It is also confronted with diffi-
culties involved in using waste paper and brokes contain-
ing calcium carbonate as materials for the production of
paper. In order to cope with these problems, papermaking
in the neutral pH range with reduced amount of alum (crude
aluminum sulfate) has been more commonly conducted.
Rosin sizing agents are usually used in conventional
papermaking systems wherein significant amount of alum is
added. The sizing 0ffect of this type of sizing agent,
especially that of a solution-type rosin sizing agent
(rosin soap sizing agent) comprising an alkali salt of a
fortified rosin, falls sharply as the addition amount of
2~8i7g6
alum is decreased and the pH of the papermaking system is
made higher up to near the neutral papermaking range. The
deterioration of the sizing effect is conspicuous when the
papermaking system contains calcium carbonate. To prevent
the deterioration of the sizing effect, addition of alum
in a large amount is necessitated after all, which lowers
the pH of the papermaking system to the acidic range,
which in turn causes degradation of the quality of paper
and other operational and economical problems.
Anionic rosin emulsion sizing agents, which can be
obtained by dispersing a fortified rosin in water as
finely divided particles with the aid of an anionic dis-
persing and emulsifying agent, exhibit more excellent
sizing effect and can be used in wider pH range than the
above-mentioned rosin soap sizing agent. Such anionic
rosin emulsion sizing agents require less amount of alum
compared with rosin soap sizing agents but they cannot
reduce the necessity of alum to such a level that the
papermaking in the neutral pH range may be carried out.
In addition, when the papermaking system contains calcium
carbonate, their sizing effect deteriorates to an unsatis-
factory level.
Cationic rosin emulsion sizing agents, which can be
obtained by dispersing a fortified rosin in water as
finely divided particles with the aid of a cationic emul-
sifying and dispersing agent, have properties of fixing
onto the pulp fiber by themselves and require less amount
of alum to develop sufficient sizing. It is also known
that they exhibit an excellent sizing effect in papermak-
ing systems of almost neutral pH range (See TAPPI Paper-
makers Conference 1988, pp 161-188).
However, improvements are still required of such
cationic rosin emulsions. That is, their preparation on a
commercial scale is relatively difficult compared with
that of conventional anionic rosin sizing agents and their
storage stability, sizing performance and foaming proper-
ties in a papermaking system containing calcium carbonate
are not satisfactory.
Under the circumstances, neutral papermaking sizing
agents for use in papermaking in the neutral range have
~~78~
been developed, examples of which include sizing agents
prepared by dispersing alkenyl succinic anhydride, alkyl
ketene dimer and the like in a dispersion medium such as
water. The major problem associated with these agents is
that they incur increase in cost for the production of
paper because either one of the above-mentioned compounds
is expensive. They also present operational problems,
being apt to cause contamination in the papermaking sys-
tem, for instance, on the press roll and the like. Fur-
thermore, they are slow to develop their sizing effect.
In addition, the sizing effect achieved by this type
of sizing agent is inferior to that of a rosin sizing
agent for high-yield pulp such as mechanical pulp.
Rosin sizing agents having an improved sizing effect
in neutral papermaking systems are proposed in Japanese
Laid-open Patent Publication Nos. 62-223393 and 62-250297
which disclose sizing agents comprising an ester compound
of a tri- or tetrahydric alcohol and a rosin compound.
Some of the drawbacks associated with these sizing agents
are that they require ester compounds in such an amount
that their content is over 20 wt% preferably 40 wt~, that
their sizing effect in acidic papermaking systems is not
satisfactory and thererfore they cannot be necessarily
suitably used in a wide pH range, and in addition, that
they incur increase in production cost since the esterifi-
cation reaction between such an alcohol and a rosin pro-
ceeds slowly and requires prolonged heating in order to
attain a sufficiently low acid value.
As described above, there is a demand for a rosin
emulsion sizing agent which rapidly develops an excellent
sizing effect in paperma]cing systems wherein the addition
of alum is limited to a low level and the pH is increased
up to around neutrality, especially in neutral papermaking
systems containing calcium carbonate and which shows
excellent mechanical and storage stabilities, and remarka-
bly reduced foaming in the papermaking system, and a
sizing method using the same.
[Brief Description of the Invention]
The present invention provides a rosin emulsion
composition for paper sizing which comprises (A) a rosi-
2~8~ 78B
nous substance containing 1.5-30 wt% of at least one
fortified or unfortified compound of an ester formed from
a rosin and at least one of a polyhydric alcohol having
not less than three hydroxyl groups per molecule, a po-
lyhydric phenol and a mixture of alcohol and/or phenol
mainly comprising polyhydric alcohol and/or phenol as
defined above and (B) a cationic poly(meth)acrylamide
having a hydrophobic group, wherein said constituent (A)
is directly dispersed in water with the aid of said con-
stituent (B) and particles in the emulsion composition
have a positive zeta potential in the range of pH 4-8 and
the accumulative median value of the weight base particle
size distribution is not more than 1 ~m.
Preferably, the constituent (A) is a rosinous sub-
stance containing 4.5-25 wt% of at least one fortified or
unfortified ester compound. More preferably, the ester
compound is a reaction product obtained by placing a rosin
and at least one polyhydric alcohol and/or phenol in a
suitable reaction vessel in such a ratio so that the molar
ratio of the carboxyl group in the former to the hydroxyl
group in the latter (-COOH/-OH) may be 0.5-50 and then
heating the mixture. The constituent (s) is, preferably,
a polymer obtained from monomers: (b-1) 2-30 mol% of a
cationic monomer, (b-2) not more than S mol% of an anionic
monomer, (b-3) 3-50 mol% of a hydrophobic monomer and (b-
4) 15-95 mol% of acrylamide and/or methacrylamide. Pre-
ferred content of the constituent (B) is 0.5-20 wt~ in the
total solids, the content of the latter being preferably
in the range of 20-60 wt%.
The present invention also provides a method of
sizing using the above described rosin emulsion paper
sizing agent.
The ester compound formed from a rosin and at least
one of a polyhydric alcohol having not less than three
hydroxyl groups per molecule, a polyhydric phenol and a
mixture of alcohol and/or phenol mainly comprising po-
lyhydric alcohol and/or phenol as defined above usable in
the present invention (hereinafter referred to as "rosin-
polyhydric alcohol/phenol ester") is an ester compound
obtained from esterification reaction accompanied with
2o8l78~
dehydration which is effected between a rosin and an
alcohol and~or phenol or a mixture thereof as defined
above and may be a completely esterified compound, a
partly esterified compound or a mixture thereof.
The fortified ester compound mentioned above is one
obtained by fortifying such an ester compound in the same
manner as fortifying a rosin compound which will be de-
scribed below.
Examples of the rosin usable in the present invention
include gum rosin, tall oil rosin, wood rosin and modified
rosins obtained from these rosins. One or two of more of
these rosins can be used singly or in combination. Exam-
ples of the modified rosin include partially or substan-
tially completely hydrogenated rosins, disproportionated
or polymerized rosins and rosins treated with formalde-
hyde.
Fortified rosins are also useful for the reaction
with the polyhydric alcohol and/or phenol. They are ob-
tained by subjecting unfortified rosins to the addition
reaction with an ~,~-unsaturated carboxylic acid. Exam-
ples of the ~,~-unsaturated carboxylic acid usable for
this purpose include fumaric acid, maleic acid, maleic
anhydride, itaconic acid, itaconic anhydride, citraconic
acid, citraconic anhydride, acrylic acid and methacrylic
acid, etc. They can be used singly or in combination.
Examples of the polyhydric alcohol having at least
three hydroxyl groups per molecule include glycerin,
trimethylolethane, trimethylolpropane, 3-methylpropane-
1,3,5-triol, pentaerythritol, diglycerin and sorbitol,
etc.
Examples of the polyhydric phenol include hydroqui-
none, pyrogarol, bisphenol-A, phenol resins and the like.
Two or more compounds selected from these polyhydric
alcohols and/or polyhydric phenols can be used in combina-
tion.
When monohydric or dihydric alcohol or monohydric
phenol are used singly in the reaction with a rosin, the
thus formed ester does not exhibit such an improved sizing
performance, etc. as is exhibited by an ester obtained
from a rosin and a polyhydric alcohol having at least
2~178~
three hydroxyl groups per molecule and/or a polyhydric
phenol but they can be used in combination with the
above-mentioned poIyhydric alcohols and/or polyhydric
phenols.
Preparation of the rosin-polyhydric alcohol/phenol
ester can be effected under conventional conditions. A
rosin and at least one alcohol and/or phenol are placed in
a suitable reactor and subjected to dehydration reaction
at an atmospheric, reduced or higher pressure, either in
the presence or absence of a catalyst at a temperature of
150-300C for 3-30 hours under agitation. Optionally,
dehydration may be azeotropically accelerated using a
solvent such as benzene, toluene and xylene.
Preferably, rosin and polyhydric alcohol and/or
polyhydric phenol are set to the reaction in a ratio
(setting ratio A) in which the rosin-poiyhydric
alcohol/phenol ester can be obtained in a high yield, i.e.
such a ratio that the molar ratio of the carboxyl group
in the former to the hydroxyl group in the latter (-
COOH(eq)/-OH(eq)) may fall in the range of 0.5-3, or
alternatively, in a ratio (setting ratio B) in which the
rosinous substance w.Lll contain the rosin-polyhydric
alcohol/phenol ester in a content of 1.5-30 wt%, i.e. such
a ratio that the above-mentioned equivalent ratio may
fall in the range of 3-50. In the former case, a rosin
compound is added afterwards so that the rosinous sub-
stance may contain the rosin-polyhydric alcohol/phenol
ester in a content of 1.5-30 wt%. In the latter case, the
mixture is subjected to dehydration reaction as it is.
COOH- portion of the above-mentioned equivalent ratio does
not include carboxyl groups derived from ~,~-unsaturated
carboxylic acid which has been added to the rosin typical-
ly to convert it to a fortified rosin.
When the equivalent ratio is less than 0.5, the
rosin-polyhydric alcohol/phenol ester contains too much
unreacted hydroxyl groups and desired effect in sizing
performance, etc. will not necessarily develop. When the
equivalent ratio is more than 50, the content of the
rosin-polyhydric alcohol/phenol ester is below 1.5 wt~,
which is generally insufficient to bring about satisfacto-
208178~
ry results.
In the present invention, the term "rosinous sub-
stance means a mixture of a rosin-polyhydric
alcohol/phenol ester and a rosin compound defined above
which contains the former in 1.5-30 wt%, preferably 4.5-25
wt%. When the content of the rosin-polyhydric
alcohol/phenol ester is less than 1.5 wt%, sizing effect
will not satisfactorily develop in a papermaking system
around the neutrality. When the content surpasses 30wt%,
the effect of improving the sizing effect in the papermak-
ing system around the neutrality will saturate while the
sizing effect in an acidic papermaking system might be
deterior~ted. Fortified rosin obtained from addition
reaction of a ~,~-unsaturated carboxylic acid to a rosin
is preferably used as a rosin compound in the rosinous
substance since it is advantageous with regard to sizing
effect.
~ or the preparation of the sizing agent of the
present invention, any of the following processes can be
adopted for incorporating the rosin-polyhydric
alcohol/phenol ester into the rosinous substance in the
above-mentioned content. That is, a reaction product
obtained by placing starting materials in a suitable
reaction vessel in a specific ratio, for example, the
above-mentioned setting ratio A and subjecting them to
heating is mixed with a rosin so that the content of the
rosin-polyhydric alcohol/phenol may fall in the above-
mentioned range and then the mixture is heated, molten and
emulsified and dispersed. Alternatively, a reaction
product obtained by placing star-ting materials in a suit-
able reaction vessel in the above-mentioned setting ratio
s and subjecting them to heating is emulsified and dis-
persed either as it is or after fortified with an ~,~-
unsaturated carboxylic acid.
The cationic poly(meth)acrylamide having a hydropho-
bic group which is used as the constituent (B) of the
sizing composition of the present invention is, prefera-
bly, a polymer obtained from monomers: (b-l) 2-30 mol% of
a cationic monomer, (b-2) not more than 5 mol% of an
anionic monomer, (b-3) 3-50 mol% of a hydrophobic monomer
20~178~
and (b-4) 15-95 mol% of acrylamide and/or methacrylamide,
which is described in Japanses Laid-open Patent Publica-
tion No. 3-227481 (1991).
When the constituent (s) is formed from monomers in a
ratio which does not fall in the above-mentioned range,
emulsifiability thereof is usually degraded or else stor-
age stability or sizing performance of the paper sizing
agent obtained therefrom tends to be inferior to the
product from monomers of the above-mentioned range.
The cationic monomer (b-l) provides poly(meth)acryla-
mide with cationicity and contributes to making the zeta
potential of the particles in the rosin emulsion positive
in the range of pH 4-8. Examples of the cationic monomer
include (mono- or di-alkyl)aminoalkyl(meth)acrylate,
(mono- or di-alkyl)amino hydroxylalkyl(meth)acrylate,
(mono- or di-alkyl)aminoalkyl (meth)acrylamide, (mono- or
di-alkyl)aminohydroxylalkylvinylether, vinylpyridine,
vinylimidazole, diallylamine, etc., and quaternary ammoni-
um salts of these monomers. These monomers can be used
singly or in combination.
Examples of the anionic monomer (b-2) include mono-
mers containing carboxylic acid radical such as
(meth)acrylic acid, maleic acid, fumaric acid, itaconic
acid, citraconic acid, crotonic acid, etc.; monomers
containing sulfonic acid radical such as vinylsulfonic
acid, (meth)allylsulfonic acid, 2-acrylamide-2-methylpro-
panesulfonic acid, sulfonated styrene, etc.; and monomers
containing phosphoric acid ester moiety such as phosphoric
acid ester of hydroxyalkyl (meth)acrylate. These monomers
can be used alone or in combination.
The reason why the above-mentioned hydrophobic
monomer (b-3) is used is basically that it provides the
polymer with hydrophobic property and improves its adsorp-
tivity to the rosin particle but we unexpectedly found
that introduction of 3-50 mol% of hydrophobic monomer as
effected in the present invention remarkably improves
emulsifiability of the rosinous substance, stability and
sizing performance of the sizing agent. Mechanism how the
hydrophobic monomer contributes to these effects is not
yet clear.
2~17~6
Examples of the hydrophobic monomer (b-3) include the
following compounds:
Acrylic acid alkyl ester or methacrylic acid alkyl
ester represented by the following formula (I):
Rl
CH2=C-COOR2 (I)
[wherein R1 represents H or methyl, R2 represents alkyl or
alkenyl having 1-22 carbon atoms, cyclohexyl, phenyl,
benzyl, glycidyl,
I ~
- C Hz ~ J
CH~ ~ CH3
[~ "
1l3C
R3
- ( CH2-CH-0 ) n_R4
(wherein R3 represents H or methyl, R4 represents H, lower
alkyl, phenyl, alkylphenyl having 1-22 carbon atoms,
aralkylphenyl having 1-22 carbon atoms, or -CH2CH2-C8F17),
or
-CH2CH(OH)-R5
~wherein R5 represents H, methyl or -CH20H
-CH2-OOC-R6
(wherein R6 represents alkyl having 1-22 carbon atoms,
alkenyl having 3-22 carbon atoms or
CI13
Cll~ ~ CH3
) } ] ,
~I ~, C:
20~1~8~
styrene and its derivative represented by the formula
(II):
R7 R~
C~z=l~ ~II)
(wherein R7 represents H or methyl, R8 represents H,
methyl or lower alkyl including -CH(CH3)2 and -C(CH3)3 ),
olefin having 6-22 carbon atoms, (meth)acrylonitrile,
vinylester such as vinyl acetate or vinyl propionate and
alkylvinylether having 1-22 carbon atoms. These monomers
can be used singly or in combination. When the monomer
constituent (b-3) is used in more than 50 mol% in the
total monomers, stability of the emulsion is degraded and
more amount of cationic poly(meth)acrylamide is required
for compensating the degradation of the stabilicy, which
in turn lead to degradation of sizing performance.
The cationic poly(meth)acrylamide having a hydropho-
bic group [constituent (B)] can be synthesized by any of
known processes. For example, the above-mentioned mono-
mers (b-l) - (b-4) are polymerized in an organic solvent
such as a lower alcohol like methanol, ethanol, isopropyl
alcohol, tert-butylalcohol, etc., acetone, methylethylke-
tone and dioxane or a mixture of one of these organic
solvents and water with the aid of a radical polymeriza-
tion catalyst. The polymer is obtained by removing the
solvent by distillation after the polymerization is fin-
ished. Radical polymerization catalysts usable in the
present invention include persulfate salts such as ammoni-
um persulfate, potassium persulfate, sodium persulfate,
redox polymerization catalysts which are a combination of
one of the above-mentioned persulfates and a reducing
agen'. Azo catalysts such as 2,2'-azo-bis-isobutyroni
trile are also usable. Optionally, conventional chain
transfer agents may be used in combination with suitable
one of these catalysts.
The viscosity of the solution of the thus obtained
polymer (B) is preferably in the range of 10 - 5000 cps,
2~817~
more preferably 50 - 2000 cps, as measured in a 20 wt%
aqueous solution by a Brookfield viscometer at 60 rpm and
25 C. With a viscosity outside of this range, the poly-
mer will be inferior in emulsifying performance for rosi-
nous substance and accordingly a greater amount of
emulsifier is needed, which deteriorates sizing perform-
ance of the resulting cationic emulsion sizing agent.
As described above, the sizing agent of the present
invention contains as basic constituents a rosinous sub-
stance containing a rosin-polyhydric alcohol and/or phenol
ester and a cationic poly(meth)acrylamide having a hydro-
phobic group. The ratio of the rosinous substance and the
cationic poly- (meth)acrylamide having a hydrophobic group
is preferably in the range in which the obtained emulsion
stands stable for a long period of time and remains stable
when added in a papermaking system or under a shearing
force applied in papermaking while keeping a satisfactory
potentiality as a sizing agent. Considering stability and
sizing performance of the product as well as economical
advantage, the cationic poly(meth)acrylamide having a
hydrophobic group is used preferably in 0.5-20 wt%, more
preferably 1-15 wt%, most preferably 3-10 wt% in tne total
solids. The effect of the polymer on the stability of the
product saturates over these upper limits and such an
excessive use of the polymer is not recommendable since it
might lead to disadvantages in cost and/or sizing perform-
ance.
The solids content in the sizing agent of the present
invention is preferably 20-60wt%, more preferably 30-50
wt%.
The sizing agent of the present invention may contain
a catinoic or nonionic surfactant if desired.
Examples of the cationic surfactant include tet-
raalkylammonium chloride, trialkylbenzylammonium chloride,
alkylamine acetate, alkylamine hydrochloride, oxyethyle-
nealkylamine, polyoxyethylenealkylamine, etc.
Examples of the nonionic surfactant include polyox-
yethylenealkyl~ther, polyoxyethylenealkylphenylether,
polyoxyethylenestyrylphenylether, aliphatic acid esters of
polyoxypropylenepolyoxyethyleneclycol glycerine, aliphatic
11
20~7g~
acid esters of sorbitan, aliphatic acid esters of polyet-
hyleneglycol, aliphatic acid esters of polyoxyethylenesor-
bitan, aliphatic acid esters of sucrose, aliphatic acid
esters of pentaerythritol, aliphatic acid esters of pro-
pylene glycol and aliphatic acid diethanolamide, etc.
Preparation of the sizing agent of the present is not
limited to a specific process. For example, in accordance
with the ~solvent process" as described in Japanese Patent
Publication No. 54-36242, a rosinous substance [constitu-
ent (A)] is dissolved in an oil-soluble solvent and mixed
with the constituent (B) and water and then the thus
~ormed mixture is passed through a homogenizer and the
solvent is removed by distillation to form an oil-in-water
type emulsion; in accordance with the ~mechanical process~
as described in Japanese Patent Publication No. 53-62680,
a rosinous substance [constituent (A)] is molten, mixed
with the constituent (B) and water and passed through a
homogenizer under high pressure at high temperature to
form an oil-in-water type emulsion; in accordance with the
process as described in Japanese Laid-open Patent Publica-
tion No. 54-77206, the constituent (A) is molten and mixed
with the constituent (B) and water under agitation to form
a water-in-oil type emulsion and then water is added
thereto to effect inversion to form an oil-in-water type
emulsion.
Average particle size of ~he emulsion of the present
invention (accumulative median value of the weight base
particle size distribution) is not more than 1 ~m, prefer-
ably not more than 0.5 ~m. When the particle size is more
than l ~m, the emulsion is apt to form sediment and is
inferior in mechanical stability. The average particle
size can be determined with Master Siser (manufactured by
Mal,vern Instruments Ltd.).
The zeta potential of the particles of the rosin
emulsion of the present invention is positive in the
range of pH 4-8. Measurement thereof can be made with
Lazer-Zee Meter Model 501 (manufactured by Pen Kem Inc.).
The sizing agent of the present invention is obtained
by dispersing and emulsifying a rosinous substance which
contains a relatively small amount (i.e. 1.5-30 wt%) of a
12
7~&
rosin-polyhydric alcohol/phenol ester with the aid of a
cationic poly(meth)acrylamide dispersant and the thus
formed sizing agent has more excellent properties than
expected by the efect of each constituent thereof: i.e.
rosin-polyhydric alcohol/phenol ester and cationic
poly(meth)acrylamide dispersant. That is, it is much more
excellent in storage and mechanical stabilities compared
with a conventional cationic rosin emulsion sizing agent
and a rosin sizing agent containing a rosin ester, exhib-
its conspicuously excellent sizing effect which cannot be
achieved by a conventional rosin sizing agent especially
in a neutral papermaking system not to mention in an
acidic papermaking system and remarkably reduces foaming
which is caused when a sizing agent is used in the paper-
making system.
As will be understood from the above description, the
sizing agent of the present invention has advantages over
conventional neutral sizing agents e.g. alkylketene dimer
or alkenyl succinic anhydride especially for use in the
bellow mentioned papermaking systems in that the former is
excellent in the sizing effect for pulp containing high-
yield pulp, rapidly develops sizing and causes less sig-
nificant contamination in the papermaking equipment such
as press roll and dryer canvas:
(1) Papermaking systems wherein the use of alum is
not allowed or limited to a low level including those for
the production of neutral machine glazed paper, neutral
liner, can liner, metal plate interleaving paper, etc.;
(2) Papermaking systems wherein waste paper contain-
ing calcium carbonate is used as material for the produc-
tion of paper including those for the production of gypsum
liner board, white board, coating base paper, groundwood-
pulp-containing paper, liner for general use, corrugating
medium, etc.;
(3) Papermaking systems where calcium carbonate is
used as filler including those for the production of
neutral printing/writing paper, neutral coating base
paper, neutral PPC paper, neutral thermographic base
paper, neutral pressure sensitive base paper, neutral
paper for ink-jet printing, neutral information paper,
13
2o8l 7~
etc.; and
(4) Papermaking systems in which the use of reten-
tion aids is restricted including those for the production
of kraft paper, etc.
The sizing agent of the present invention also exhib-
its an excellen~ sizing effect in papermaking systems in
which alum (crude aluminum sulfate) is used in a relative-
ly large amount.
According to the sizing method of the present inven-
tion, the rosin emulsion sizing agent of the present
invention is added to the papermaking system, for example,
at the wet end in the production process of paper or
paperboard. Specifically, the sizing agent is added to an
aqueous dispersion of pulp fibers preferably in an amount
of 0.005 - 10 % , more preferably 0.05 - 5 %, as weight of
the solids in the agent by dry weight of the dispersion.
In preparing the above-mentioned various types of
paper and paperboard, bleached or unbleached chemical pulp
such as kraft pulp and sulfite pulp; bleached or un-
bleached high yield pulp such as groundwood pulp, mechani-
cal pulp and thermomechanical pulp; waste paper such as
waste newspaper, waste magazine paper, waste corrugated
board and deinked waste paper can be used. Mixture of such
pulp material and asbestos, polyamide, polyester, polyole-
fin and the like are also useful.
Optionally, additives such as fillers, dyes, dry-
strength agents, wet-strength agents, retention aids and
drainage aids may be used for providing the paper or
paperboard with specifically desired properties. Examples
of the filler include clay, talc and ground or precipitat-
ed calcium carbonate, which can be used singly or in
combination.
Examples of the dry- strength agent include anionic
polyacrylamide, cationic polyacrylamide, amphoteric polya-
crylamide, cationized starch, etc., which can be used
singly or in combination.
Examples of the wet-strength agent include
polyamide-epichlorohydrin resins, melamine-formalin re-
sins, urea-formalin resins, etc., which can be used singly
or in combination with anionic polyacrylamide. Examples
14
- 2081~
of the retention aid include anionic or cationic high-
molecular weight polyacrylamide, combination of silica sol
and cationized starch, combination of bentonite and ca-
i tionic high-molecular weight polyacrylamide, etc.
Examples of the drainage aid include polyethylenei-
mine, cationic polyacrylamide, etc. Optionally, starch-
es, polyvinyl alcohol, dyes, coating colors, surface
sizing agents, antislipping agents, etc. may be applied
using a size press, gate roll coater, Billblade coater,
calender, etc.
Alum is added before, after or simultaneously with
the addition of the sizing agent of the present invention.
Additives and rosins mentioned above may be incorpo-
rated into the sizing agent, if necessary, which can be
carried out simultaneously with or separately from the
addition of the rosinous substance containing the rosin-
polyhydric alcohol/phenol ester in the same or different
way.
The rosin sizing agent of the present invention is
also usable as a surface sizing agent. In this case, it
is applied on wet paper which has been made by any of the
conventional methods such as spraying, dipping, coating
and the like.
[Embodiment of the Invention]
The following examples of the preparation of rosin
polyhydric alcohol/phenol esters and the demonstrative and
comparative examples of the sizing agent illustrate the
present invention more specifically. These examples,
however, should not be taken as limiting the present
invention. Part and % in the following examples are
based on weight, unless contrarily mentioned.
(1) Preparation of rosin-polyhydric alcohol/phenol ester
Rosin-polyhydric alcohol/phenol esters (A-1) - (A-11) (for
working examples) and (A-12) - (A-14) (for comparative
examples) were prepared in the following manner.
(1)-1 Preparation of (A-1)
600 parts of a gum rosin (acid value: 170) and 55
parts of glycerin (equivalent ratio: -COOH/-OH = 1.0) and
0.2 part of phosphoric acid were placed in a flask (vol-
ume: one liter) equipped with a stirrer, a thermometer, a
20817~
nitrogen-introducing port and a condenser, heated under
nitrogen flow until the temperature reached 270C and kept
at the temperature for 15 hours to give the rosin-polyhy-
dric alcohol/phenol ester (A-l).
The acid value of the product was 17 and if this is
attributable to the acidity of the gum rosin having an
acid value of 170, the content of unreacted gum rosin in
the reaction mixture is about 10%, from which the content
of the rosin-polyhydric alcohol/phenol in the reaction
mixture is calculated as about 90%. In the following
examples, the content of ester compound is calculated in
the same manner.
(1)-2 Preparation of (A-2)-(A-ll) and (A-12)-(A-13)
Rosin-polyhydric alcohol/phenol esters (A-2)-(A-11)
and (A-12) and (A-13) were prepared in the same manner as
described about (A-1) from rosins and polyhydric alcohols
and phenols summarized in Table 1.
(1)-3 Preparation of (A-14)
In accordance with the process described in Japanese
Laid-open Patent Publication No. 62-223393, rosin-polyhy-
dric alcohol ester (A-14 ) was prepared as follows .
100 parts of a gum rosin (acid value: 170) and 8
parts of
glycerin were placed in a flask (volume: one liter)
equipped with a stirrer, a thermometer, a nitrogen-intro-
ducing port and a condenser, reacted at 250C for 12
hours to give the rosin-polyhydric alcohol ester (A-14).
(2) Preparation of fumaric-acid fortified rosin
Fumaric acid fortified rosins (F-l) - (F-4) (for
working examples) and (F-5) (for comparative examples)
were prepare~ in the following manner.
16
2Q8178~
Table l
-
Rosin-polyhydric alcohol/phenol ester
Reaction Rosin Polyhydric Init. Eq. Ester Acid
Product Alcohol or Ratio Content Value
Phenol(COOH/OH) (~)(mg/g)
A- 1 Gum rosin Glycerin 1.0 90 17
A- 2 Gum rosin Glycerin 0.5 86 23
A- 3 Gum rosin Glycerin 2.0 67 56
A- 4 Gum rosin Glycerin 20 5 161
A- 5 Gum rosin Glycerin 50 2 167
A- 6 Fortified rosin Glycerin 2.5 70 104
A- 7 Tall oil rosin Glycerin 1.0 86 24
A- 8 Gum rosin Trimethylol 1.0 77 39
propane
A- 9 Gum rosin Pentaerythytol 1.0 82 31
A-10 Gum rosin Sorbitol 0.5 54 78
A-ll Gum rosin Bisphenol-A l.O 80 34
A-12 Gum rosin Glycerin 0.4 92 13
A-13 Gum rosin Glycerin 80 1 168
A-14 Gum rosin Glycerin 1.2 82 35
-
* Initial equivalent ratio of -COOH in the rosin to -OH
in the alcohol or phenol.
** Fortified rosin (F-l) (see below)
17
2~817~1~
(2)-1 Preparation of (F-l)
70 parts of fumaric acid were slowly added to 460
parts of a molten gum rosin (acid value: 170) at about 200
C. After the reaction was almost completed, 470 parts of
tall oil rosin modified by formaldehyde (modification
rate: 3 %) were added and the molten reaction mixture was
further stirred to be homogeneous and then allowed to cool
to room temperature. The thus obtained reaction product
(F-l) was a fortified rosin to which 7 ~ of fumaric acid
were added.
(2)-2 Preparation of (F-2) [product of the reaction
between (A-l) and fumaric acid]
465 parts of the reaction product of a rosin and a
polyhydric alcohol (A-1) obtained in above (1)-2 were
heated to 200 C to be molten. 35 parts of fumaric acid
was added thereto and the mixture were kept at 200C for 3
hours. The thus obtained product of the reaction with
fumaric acid designated as (F-2) contained about 90% of a
rosin-polyhydric alcohol ester, which is substantially the
same as the content of a rosin-polyhydric alcohol ester in
the above-described product (A-l ) .
(2)-3 Prep~ration of ( F-3 ) [product of the reaction
between (A-~) and fumaric acid], (F-4)[product of the
reaction between (A-5) and fumaric acid] and (F-5)
[product of the reaction between (A-13) and fumaric acid],
Rosin-polyhydric alcohol esters (A-4), (A-5) and (A-
13) were respectively treated with fumaric acid in the
same manner as described about (F-2) and reaction product
(F-3) - (F-5) were prepared. These product contained a
rosin-polyhydric alcohol ester in about 5%, about 2% and
about 1% respectively.
(3) Preparation of cationic poly(meth)acrylamide disper-
sant having a hydrophobic group
In accordance with a working example described in
Japanese Laid-open Patent Publication No. 3-227481,
cationic poly- (meth)acrylamide dispersant having a hydro-
phobic group (B-l)-(B-2) (for working examples) were
prepared as follows.
(3)-1 Preparation of (B-1)
31.4 parts of dimethylaminoethyl methacrylate, 85.3
18
2~ 7~6
parts of a 50 ~ aqueous solution of acrylamide, 20.8 parts
of styrene, 100.6 parts of deionized water, 143.3 parts of
isopropyl alcohol and 0.6 part of n-dodecylmercaptan were
placed in a four-necked flask (volume: one liter) equipped
with a stirrer, a thermometer, a condenser and a
nitrogen-introducing port. The pH o~ the mixture was
adjusted to 4.5 with a 20 % acetic acid aqueous solution.
The mixture was stirred and warmed to 60C under nitrogen
atmosphere. 2.3 parts of a 5 % aqueous solution of ammo-
nium persulfate were added thereto and the temperature of
the mixture was raised to 80C. After the mixture was
kept at the temperature for l-.5 hours, 0.7 part of the 5 %
aqueous solution of ammonium persulfate was added. After
the reaction mixture was maintained at the same tempera-
ture for another hour, 100 parts of deionized water were
added and the isopropyl alcohol was removed by distilla-
tion.
The polymer solution was diluted with deionized water
after the distillation was finished. The thus obtained
cationic polyacrylamide B-1 dispersant was a polymer
solution containing 20.4% solids and having a Brookfield
viscosity (hereinafter referred to as viscosity) of 340
centipoise (cps) measured at 25C and 60rpm.
(3)-2 Preparation of (B-2)
Polyacrylamide dispersant (B-2) was prepared in the
same manner as described about (B-1) by polymerizing 12
parts of dimethylaminopropyl methacrylamide, 2 parts of
methacrylic acid, 144 parts of a 50 % aqueous solution of
acrylamide, 8 parts of iso-butyl methacrylate, 0.5 part of
n-dodecylmercaptan in a mixture of iso-propylalcohol-water
using ammonium persulfate as a catalyst. The thus ob-
tained cationic polyacrylamide B-2 dispersant was a poly-
mer solution containing 20.2% solids and having a viscosi-
ty of 590cps.
(4) Preparation of anionic polymer dispersant (B-3)
An anionic polymer dispersant (B-3) was prepared as
follows in accordance with the process described in Refer-
ential Example lO of Japanese Laid-open Patent Publication
NO. 61-108796 (1986).
55 parts of styrene, 30 parts of methacrylic acid, 5
19
2~l7~
parts of itaconic acid, 10 parts of lauryl acrylate, 50
parts of 10 % sodium naphthalenesulfonate-formalin conden-
sate, one part of ammonium persulfate and 200 parts of
water were stirred and mixed and heated at 150C under
pressure for 30 minutes. The mixture was allowed to cool
to 70C and 35.5 parts of 48.5 % of sodium hydroxide and 7
parts of water were slowly added thereto. Then the mix-
ture was stirred for 30 minutes and allowed to cool to
room temperature. The thus obtained anionic polymer
dispersant s-3 was a dispersion of saponified copolymer of
styrene and methacrylic acid containing 30 % solids.
(5) Preparation of paper sizing agents
(5)-1 Example 1
20 parts of the above-mentioned rosin-polyhydric
alcohol ester (A-l) obtained in (1)-1 and 80 parts of
fumaric acid fortified rosin (F-l) were mixed and molten
by heating to about 150 C. 25 parts of cationic
poly(meth)acrylamide dispersant (B-l) were added thereto
under vigorous agitation to form a water-in-oil emulsion.
Hot water was slowly added to the thus obtained
emulsion to convert the emulsion into the oil-in-water
type. Hot water was further added quickly to stabilize
the resulting oil-in-water type emulsion and the emulsion
was allowed to cool to room temperature.
The thus obtained emulsion contained 50.3 % solids
and the accumulative median particle size measured with a
Master Sizer (manufactured by Malvern Instruments Ltd.)
was 0.38 ~m. The emulsion was stable for a long period of
time.
(5)-2 Examples 2-12 and 17
In the same manner as in Example 1, rosin emu~sion
paper sizing agents (Examples 2-12 and 17) werc prepared
from 100 parts of molten mixture of the above-mentioned
rosin and polyhydric alcohol ester (A-l)-(A-3), (A-6),
~A-ll), (A-12) and (F-2)-(F-4) and fumaric acid fortified
rosin (F-1) in the blending ratio summarized in Table 2
using 25 parts of the above-mentioned polyacrylamide
dispersant (B-l).
5-(3) Examples 13 and 14
Respectively 30 parts of the rosin-polyhydric alcohol
2û8~
esters (A-7) and (A-8) and 120 parts of the above-men-
tioned fumaric-acid fortified rosin (F-1) were molten and
mixed at 170 C and admixed with 39 parts of the above-
mentioned polylacrylamide dispersant (B-l) and 205 parts
of water at an elevated temperature and under high pres-
sure. The mixture was made to pass through an industrial
homogenizer under a pressure of about 150kg/cm2 twice.
The thus obtained rosin emulsion sizing agents respective-
ly contained about 40 % solids.
5-(4) Examples 15 and 16
30 parts of the rosin-polyhydric alcohol esters (A-9)
and (A-10) and 120 parts of the above-mentioned fumaric-
acid fortified rosin (F-1) were dissolved in 150 parts of
toluene and mixed with 39 parts of the above-mentioned
polylacrylamide dispersant (B-2) and 345 parts of water.
The mixture was made to pass through an industrial homoge-
nizer under a pressure of about 150kg/cm2 twice and the
toluene was completely removed by vacuum distillation.
The thus obtained rosin emulsion sizing agents respective-
ly contained about 35 % solids.
(5)-5 Comparative ~xamples 1-7
In the same manner as in Example 1, rosin emulsion
sizing agents were obtained from rosin-polyhydric alcohol
ester and fumaric-acid fortified rosin (F-l) (total
amount: 100 weight parts) in a blending ratio shown in
Table 2 using 25 parts of the above-mentioned
poly(meth)acrylamide dispersant (B-l) or 16 parts of (B-
3).
(5)-6 Comparative Example 8 [an example wherein an anion-
ic dispersant is used]
Rosin-polyhydric alcohol ester (A-14) and fumaric-
acid fortified rosin (F-l) (total amount: 150 weight
parts) in a blending ratio shown in Ta~le 2 were dis-
solved in 150 parts of toluene and mixed with 15 parts of
a 30% aqueous solution of sodium dodecylbenzenesulfonate
(B-4) and 275 parts of water. The mixture was made to
pass through an industrial homogenizer under a pressure of
about 150kg/cm2 twice and the toluene was completely
removed by vacuum distillation. The thus obtained rosin
emulsion sizing agent contained 35.1 % solids.
21
20817~
The compositions and properties of these working and
comparative examples are summarized in Table 2.
Table 2
Rosin Content Ratio
Polyhydric in Rosinous Substance Dis- SizinQ AQent
Alcohol/ Rosin- Fortified persant Av. Zeta SolidsPhenol Polyhydric Rosin Particle Potential (~) Alcoholl (F-l) Size(~m) (mV)
Phenol
.. . . . ... _
1 A- 1 20 80 B-l0.38 +36 50.3
2 A- 2 20 80 B-l0.40 +33 50.1
3 A- 3 Z0 80 B-l0.38 -~35 50.3
4 F- 2 20 Bo B-l0.42 +32 50.2
s F- 2 lOO o B-l0.40 +31 50.7
6 F- 3 100 0 B-l0.39 +29 50.5
7 A- 1 2 98 B-l0.40 +28 50.2
Ex.8 A- 1 5 95 B-l0.39 +30 50.5
9 A- 1 28 72 B-l0.38 +37 50.3
A- 1 33 67 B-l0.37 +36 51.4
11 A- 6 20 80 B-l0.40 +33 50.2
12 A-ll 20 80 B-l0.42 +32 50.1
13 A- 7 20 80 B-l0.40 +35 40.5
14 A- 8 20 80 B-l0.41 +34 40.1
A- 9 20 80 B-20.43 +35 35.4
16 A-10 20 80 B-20.42 +33 35.2
17 A-12 20 80 B-l0.41 +28 50.4
_ _ .
1 F- 5 100 0 B-l0.40 +25 50.3
2 A- 1 1 99 B-l0.42 +26 49.5
3 A- 1 50 50 B-l0.45 +35 50.6
Comp. 4 - 0 100 B-l 0.42 +25 50.5
Ex.5 - 0 100 B-30.30 -48 50.7
6 A- 1 20 80 B-30.35 -50 50.0
7 A- 1 50 50 B-30.41 -53 50.1
8 A-14 50 50 B-40.39 -50 35.1
22
2~8~ 7~
Sizing effect of these working and comparative exam-
ples were tested in the following test conditions, results
of which are summarized in Table 3.
The amount of the agents used in the tests are de-
scribed in weight ratio of solids to the absolutely dried
weight of pulp.
(6) Sizing effect test
(6)-l Sizing effect test 1
Bleached kraft pulp (mixture of soft wood pulp and
hard wood pulp in the ra~io of 1 : 4) was beaten with a
beater in diluting water of lOOppm hardness till the
Canadian standard freeness thereof reached 350ml. The
amount of water was such that the pulp consistency thereof
was 2.5%.
1.2 liter of the pulp slurry was placed in the break-
er and 0.2 % of the sizing agent of the examples or com-
parative examples and 2.0 % of alum were simultaneously
added thereto. Then the pH cf the slurry was adjusted to
4.5 with caustic soda. After the mixture was stirred for
30 minutes, the pulp slurry was diluted with diluting
water of pH 4.5 to a consistency of 0.25 % and 0.05 % of a
cationic polyacrylamide retention aid ("Epinox DS 510"
marketed by DIC-Hercules Chemicals, Inc.) was added. From
the thus prepared paper stock (temperature: 40C), test
paper having a basis weight of 65 g/m2 was made using a
Noble and Wood papermachine. The wet test paper was dried
at 100C for 60 seconds by a drum dryer.
After conditioned in an atmosphere of fixed tempera-
ture and humidity (20C and 60 %RH) for 24 hours, the
sizing degree was measured by the Stockigt method.
The conditions of this sizing effect test correspond
to those of a acidic papermaking system in which the pH is
in an acidic range with the use of alum.
(6)-2 Sizing effect test 2
1.2 liter of the pulp slurry beaten in the same
condition as in the above-mentioned sizing effect test 1
was placed in the breaker and 0.4 % of the sizing agent of
the examples (or comparative examples) and 0.2 % of crude
alum were simultaneously added thereto. Then the pH of
the slurry was adjusted to 7.5 with caustic soda. After
23
~08I7~&
the mixture was stirred for 30 minutes, the pulp slurry
was diluted with diluting water of pH 7.5 to a consistency
of 0.25 % and 0.05 % of a cationic polyacrylamide reten-
tion aid (~'Epinox DS 510~ marketed by DIC-Hercules Chemi-
cals, Inc.) was added. From the thus prepared paper stock
(temperature: 40C), test paper having a basis weight of
65 g/m2 was made using a Noble and Wood papermachine. The
wet test paper was dried at 100C for 60 seconds by a
drum dryer.
After conditioned in an atmosphere of fixed tempera-
ture and humidity (20C and 60 %RH) for 24 hours, the
sizing degree was measured by the Stockigt method.
The conditions of this sizing effect test correspond
to those of a papermaking system in which the use of crude
alum is limited to a low level for making neutral machine
glazed paper and metal plate interleaving paper, etc.
(6)-3 Sizing effect test 3
1.2 liter of the pulp slurry prepared in the same
manner as in the above-mentioned Sizing effect test 1 was
placed in a breaker and 0.5 % of the sizing agent of the
examples (or comparative examples), 1.0 ~ of alum and 0.2
% of the above-mentioned DS 510 dry-strength/retention
aid were added. After the mixture was stirred for 10
minutes, the pulp slurry was diluted to a consistency of
0.25 % with diluting water of pH 8 and 10 % of precipitat-
ed calcium carbonate ("Tamapearl 121S" marketed by Okutama
Industry Co., Ltd.) and 0.01 % of a cationic polyacryla-
mide retention aid ("Hi Reten 104" marketed by DIC-Her-
cules Chemicals, Inc.) were added thereto. From the thus
prepared paper stock (temperature: 40C), test paper
having a basis weight of 65 g/m2 was made using a Noble
and Wood papermachine. The wet test paper was dried at
100C for 60 seconds with a drum dryer. After conditioned
in an atmosphere of fixed temperature and humidity (20C
and 60 %RH) for 24 hours, the sizing degree was measured
by the Stockigt method.
The conditions of this sizing effect test correspond
to those of a papermaking system in which calcium carbon-
ate is used as filler for making neutral printing/writing
paper, neutral coating base paper, neutral PPC paper and
24
20~78~
neutral thermographic paper, neutral pressure sensitive
paper and neutral information paper, etc.
(6)-4 Sizing effect test 4
waste corrugated board was beaten with a beater in
diluting water of lOOppm hardness till the Canadian
standard freeness thereof reached 400ml. The amount of
water was such that the pulp consistency thereof was 2.5%.
1.2 liter of the pulp slurry was placed in a breaker and
0.2 ~ of the sizing agent of the examples (or comparative
examples) was added. After the mixture was stirred for 10
minutes, the pulp slurry was diluted to a pulp consistency
of 0.25 % and 0.05 % of the above-mentioned DS 510 was
added. From the thus prepared paper stock (temperature:
40C), test paper having a basis weight of 100 g/m2 was
made using a Noble and Wood papermachine. The wet test
paper was dried at 100C for 80 seconds with a drum
dryer. After conditioned in an atmosphere of fixed tem-
perature and humidity (20c and 60 ~RH) for 24 hours, the
sizing degree was measured by the one-minute Cobb method.
The conditions of this sizing effect test correspond
to those of a papermaking system in which the use of crude
alum is not allowable for making neutral liner and can
liner, etc.
(6)-5 Sizing effect test 5
A mixture of waste coated paper and bleached hard
wood pulp in a mixing ratio of 1 : 4 was beaten with a
beater in diluting water of lOOppm hardness till the
Canadian standard freeness thereof reached 350ml. The
amount of water was such that the pulp consistency thereof
was 2.5%. The content of calcium carbonate in the pulp
slurry was 7 % based on the weight of the dried pulp.
1.2 liter of the pulp slurry was placed in a breaker
and 0.5 % of crude alum was added thereto. ~fter the
mixture was stirred for 1 minute, the pulp slurry was
diluted to a consistency of 0.25 % and 0.5 % of the
sizing agent of the examples (or comparative examples) and
0.05 % of the above~mentioned DS 510 was added thereto.
From the thus prepared paper stock, test paper having a
basis weight of 80 y/m2 was made using a Noble and Wood
papermachine. The wet test paper was dried at 100C for
7 8 ~
70 seconds with a drum dryer. After conditioned in an
atmosphere of fixed temperature and humidity (20C and 60
~RH) for 24 hours, the sizing degree was measured by the
one-minute Cobb method.
The conditions of this sizing effect test correspond
to those of a papermaking system containing calcium car-
bonate which has come from waste paper materials for
making gypsum liner board and white board, etc.
The results of foaming properties test, mechanical
stability test and storage stability test are summarized
in Table 4.
(7) Foaming properties test
0.6 ~ of the above-mentioned sizing agent of each
example or comparative example and 0.25 ~ of alum were
simultaneously added to the pulp slurry which had been
prepared as in the above-mentioned Sizing effect test 1
and the pH of the mixture was adjusted to 7.5 with caustic
soda. After the mixture was stirred for 3 minutes, the
pulp slurry was diluted to 0.25 % with diluting water of
pH 7.5 and 0.05 % of DS 510 was added thereto. The mix-
ture was stirred for another minute and placed in a
cylindrical vessel. The pulp slurry was made to circulate
by continuously pumping up a small amount of the slurry
and dropping it from above one meter onto the surface of
the slurry left in the vessel. The area where accumula-
tion of foam was observed was measured after 10 minutes'
circulation. The percent ratio of the foaming area to the
total surface area was calculated (The temperature of the
tested pulp slurry was 40 C).
(8) Mechanical stability test
50 g of the above-mentioned sizing agents of the
examples and comparative examples were respectively placed
in a cup and subjected to the Marlon stability test for 5
minutes under the conditions: temperature: 25C, loading
pressure: 20kg, and rotation rate: 800rpm. Then the
sample was filtered through a mesh (mesh size: 325) and
the weight of the fil-tration residue was determined and
the weight percentage of the residue to the total solids
was calculated.
(9) Storage stability test
26
2~8~7~
lOOml of the above-mentioned sizing agents of the
examples and comparative examples were respectively
placed in a test tube (length: 30 cm; inner diameter: 2.1
cm). After the samples were allowed to stand for two
months, the thickness (mm) of the sediment settled on the
bottom was measured.
As described above, the rosin emulsion sizing agent
of the present invention formed of an aqueous rosin emul-
sion obtained by dispersing and emulsifying a rosinous
substance containing a rosin-polyhydric alcohol/phenol
ester with the aid of a cationic poly(meth)acr~lamide
dispersant is excellent in storage and mechanical stabili-
ties, exhibits conspicuously excellent sizing effect which
cannot be achieved by a conventional rosin sizing agent
not only in an acidic papermaking system but also in a
neutral papermaking system and remarkably reduces foaming
which is caused when a sizing agent is used in the paper-
making system.
208~7~
Table 3
Sizing Fffect of Sizing Agents
Stockigt Size (sec) Cobb Size (g/m2)
Test 1 Test 2 Test 3 Test 4 Test 5
1 32 24 25 35 24
2 31 18 19 45 32
3 31 23 23 38 26
4 33 23 26 36 23
33 17 12 53 38
6 34 13 10 60 42
7 33 14 12 60 40
Ex.8 32 19 15 50 35
9 31 26 26 33 22
31 26 27 34 22
ll 33 20 20 40 29
12 31 21 23 38 26
13 32 22 24 37 26
14 32 24 23 36 28
31 23 21 38 25
16 33 21 19 43 27
17 30 14 11 61 41
1 29 4 2 72 52
2 29 6 3 68 49
3 19 20 18 46 36
Comp. 4 30 7 1 71 50
Ex.5 30 0 0 140 110
6 25 6 6 78 71
7 18 11 9 65 47
8 15 9 7 69 55
. . _
2D81 786
Table 4
Properties of Sizing Agent
Storage Mechanical Foaming
Stability Stability (%)
(mm) (%)
1 <1 0.2 10
2 1 0.3 20
3 <1 0.2 10
4 <1 0.2 10
2 0.3 30
6 2 0.4 40
7 2 0.4 30
Ex. B 1 0.3 20
9 <1 0.2 10
1 0.2 10
11 1 0.3 20
12 1 0.3 20
13 1 0.2 10
14 2 0.3 20
2 0.3 20
16 1 0.4 10
17 2 0.4 40
l 5 0.6 70
2 4 0.6 60
3 6 0.5 30
Comp.4 4 0.5 80
Ex. 5 3 0.6 80
6 4 0.6 80
7 5 0.7 70
8 6 1.2 90
-
29
