U.S. patent number 3,925,328 [Application Number 05/412,350] was granted by the patent office on 1975-12-09 for surface sizing compositions.
This patent grant is currently assigned to Sanyo Chemical Industries, Ltd.. Invention is credited to Yasuo Shibahara, Yoichi Tominaga.
United States Patent |
3,925,328 |
Shibahara , et al. |
December 9, 1975 |
Surface sizing compositions
Abstract
A surface sizing composition for paper which comprises a
copolymer of styrene and at least one unsaturated carboxylic
compound selected from the group consisting of maleic acid, maleic
anhydride and half-esters of maleic acid, wherein the copolymer has
a carboxylate equivalent of 80 - 300 based on the free carboxylic
acid form, and wherein the copolymer has 5 - 50% of its total
carboxylic groups as alkali metal salts and 95 - 50% of its total
carboxylic groups as at least one non-metal salt selected from the
group consisting of ammonium salts and lower alkyl amine salts.
Inventors: |
Shibahara; Yasuo (Kyoto,
JA), Tominaga; Yoichi (Kyoto, JA) |
Assignee: |
Sanyo Chemical Industries, Ltd.
(Kyoto, JA)
|
Family
ID: |
14653621 |
Appl.
No.: |
05/412,350 |
Filed: |
November 2, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Nov 15, 1972 [JA] |
|
|
47-115078 |
|
Current U.S.
Class: |
524/52; 8/115.6;
8/119; 162/168.1; 162/168.2; 162/168.6; 162/168.7; 427/326;
524/272; 525/327.6; 525/329.6; 524/53; 524/549; 525/327.8 |
Current CPC
Class: |
D21H
17/28 (20130101); D21H 17/36 (20130101); D21H
17/43 (20130101); C08L 35/00 (20130101); D21H
17/35 (20130101); C09J 135/06 (20130101); D21H
17/34 (20130101) |
Current International
Class: |
D21H
17/00 (20060101); D21H 17/28 (20060101); D21H
17/43 (20060101); D21H 17/36 (20060101); D21H
17/34 (20060101); D21H 17/35 (20060101); C08L
35/00 (20060101); C09J 135/06 (20060101); C09J
135/00 (20060101); C08F 008/44 () |
Field of
Search: |
;260/78.5T,17.4ST,27R
;162/168 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kight, III; John
Attorney, Agent or Firm: Oblon, Fisher, Spivak, McClelland
& Maier
Claims
What is claimed as new and desired to be secured by Letters Patent
of the United States is:
1. A surface sizing composition for paper, which comprises:
a copolymer of styrene and at least one unsaturated carboxylic
compound selected from the group consisting of maleic acid, maleic
anhydride and half esters of maleic acid, wherein said copolymer
has a carboxylate equivalent of 80 - 300 based on the free
carboxylic acid form, and wherein said copolymer has 5 - 50% of its
total carboxylic groups as alkali metal salts and 95 - 50% of its
total carboxylic groups as at least one non-metal salt selected
from the group consisting of ammonium salts and lower alkyl amine
salts.
2. The surface sizing composition of claim 1, wherein the molar
ratio of styrene to the unsaturated carboxylic compound is 30 - 90
: 70 - 10.
3. The surface sizing composition of claim 2, wherein said molar
ratio is 45 - 60 : 55 - 40.
4. The surface sizing composition of claim 1, wherein the
carboxylate equivalent is 100 - 240.
5. The surface sizing composition of claim 1, wherein said
copolymer has 10 - 25% of its total carboxylic groups as alkali
metal salts and 90 - 75% of its total carboxylic groups as a
non-metal salt.
6. The surface sizing composition of claim 1, wherein said
half-esters of maleic acid are half-esters of maleic acid with
monohydric aliphatic alcohols containing 1 - 20 carbon atoms.
7. The surface sizing composition of claim 1, wherein said alkali
metal salt is the sodium salt or potassium salt.
8. The surface sizing composition of claim 1, wherein sad non-metal
salt is an ammonium salt.
9. The surface sizing composition of claim 1, wherein the lower
alkyl ammonium salts are monoalkyl amines, dialkylamines or
trialkyl amines which have 1 - 3 carbon atoms in each alkyl
group.
10. The surface sizing composition of claim 1, wherein the
copolymer has an additional structural unit derived from an
ethylenically unsaturated monomer.
11. The surface sizing composition of claim 10, wherein the
ethylenically unsaturated monomer is an acrylate or methacrylate
having 4 - 12 carbon atoms.
12. The surface sizing composition of claim 1, wherein the free
carboxylic acid content of the copolymer is less than 45% of the
total carboxylic groups.
13. The surface sizing composition of claim 1, which further
comprises a modifier.
14. The surface sizing composition of claim 13, wherein said
modifier is a starch, a polyvinyl alcohol, a rosin or a petroleum
resin.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to surface sizing compositions for paper
making. More particularly, this invention relates to stable surface
sizing compositions which have excellent heat, mechanical and alum
resistance during surface sizing. As used herein the term
"carboxylic group" is intended to include carboxylate salts and the
anhydride structure in addition of course, to the free carboxylic
acid group. Of course, an anhydride group is the group which
results from the condensation of two carboxylic groups.
2. Description of the Prior Art
Surface sizing compositions are usually applied to paper in a size
press. Different types of size presses are used according to how
the rolls of paper are arranged and the method by which sizing
solution is applied to the paper. Verticle size presses are made up
of top and bottom rolls located one over the other, and horizontal
size presses consist of two rolls placed side by side. Recently,
inclined size presses have been principally used which contain two
rolls placed obliquely, and which apply sizing solution to the
paper by placing the sizing solution into the dam formed by the two
rolls.
Paper is commonly surface-sized by means of a size press as
follows: The paper sheet is semi-dried beforehand or is dried by
driers positioned just before the size press runs through the dam
of the sizing solution at a high speed. It is run between two press
rolls under a high nip pressure, and then the treated sheet is
dried by driers which are located just beyond the size press.
Surface sizing has some advantages. For example, it leads to
substantial savings in sizing costs and to improvement in paper
quality compared to internal sizing techniques because almost all
of the sizing composition is retained on the surface of the paper
during surface sizing. During surface sizing by the size press,
however, the sizing solution suffers heat and mechanical shock
which is generated during the operation. In addition, aluminum
salts such as alum elute from the paper into the sizing solution.
These salts are used in the wet end of the sheeting step. These
eluted salts have some adverse effects on the sizing solution
because they facilitate precipitation of materials from the sizing
solution. Because of the operational difficulties encountered in
the sizing process, the sizing agent which is the main ingredient
of the sizing solution should be stable to heat mechanical shock
and be able to resist the aluminum salts in order to give the paper
the proper amount of water resistance and writing quality.
Heretofore, various surface sizing compositions have been proposed
and used. They have not been satisfactory, although some of them
have a few advantages. In continuous sizing operations, sizing
solutions which contain conventional sizing compositions gradually
lose their solubilizing properties because of the heat, mechanical
shock and aluminum salts to which they are exposed. This gradually
results in the formation of scum. The presence of the scum causes a
decrease in the sizing effect of the sizing solution, and has an
adverse effect on the appearance of the treated paper because of
the presence of the scum on the surface of the paper. Because of
these disadvantages surface sizing compositions have enjoyed
limited use in the field of paper making.
A need, therefore, continues to exist for a surface sizing
composition which has none of the disadvantages of the prior art
sizing compositions and which is stable to mechanical shock and
heat.
SUMMARY OF THE INVENTION
Accordingly, one object of this invention is to provide a surface
sizing composition having improved properties.
Another object of this invention is to provide a surface sizing
composition having good stability under operating conditions.
Yet another object of this invention is to provide a surface sizing
composition which yields paper having improved properties at low
cost.
Briefly, these objects and other objects of the invention as
hereinafter will become more readily apparent can be attained by a
surface sizing composition which comprises a copolymer of styrene
and at least one unsaturated carboxylic compound selected from the
group consisting of maleic acid, maleic anhydride and half-esters
of maleic acid, wherein the copolymer has a carboxylate equivalent
of 80 - 300 based on the free carboxylic acid form, and wherein the
copolymer has 5 - 50% of its total carboxylic groups as alkali
metal salts and 95 - 50% of its total carboxylic groups as at least
one non-metal salt selected from the group consisting of ammonium
salts and lower alkyl amine salts.
BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the composition of the invention the carboxylate equivalent of
the copolymer as the free acid must be 80 - 300, preferably 100 -
240, wherein the carboxylate equivalent means the molecular weight
of the copolymer (reduced to the free acid basis) per carboxylate
group. A copolymer with a value less than 80 exhibits inadequate
sizing effects, while if the copolymer has a value greater than 300
the sizing effect and the solubility of the copolymer in water
decreases. When the copolymer is used under severe sizing
conditions such as long continuoius operation at severe pH values,
it is preferred to use copolymers which have relatively low
equivalents within the range of 80 to 300, because lower
carboxylate equivalents bring about better solubility of the
copolymer in water. Furthermore, the carboxylate groups in the
copolymer must be present in the form of specific salts in order to
attain the objects of this invention. Thus, 5 - 50% of the total
carboxylate groups must exist as an alkali metal salt, and 95 - 50%
of the total carboxylate groups must exist in the form of at least
one salt selected from the group consisting of ammonium salts and
lower alkyl amine salts. If the copolymer contains less than 5%
alkali metal salts, the resulting copolymer does not have enough
stability when used in the size press. If the copolymer has an
alkali metal salt content greater than 50% the high salt content
has an adverse effect on the sizing effects of the copolymer. When
the sizing effects and the stability of the copolymer are
considered it is preferred that the alkali metal salt be from 10 -
25%. However, if the stability characteristics of the copolymer are
to be emphasized, it is preferable to use a copolymer having an
alkali metal salt content within the higher regions of the 5 - 50%
range. The copolymer also has a carboxylate group content as the
ammonium and lower alkylamine salts preferably ranging from 90 -
75% of the total carboxylate group content. The copolymer
preferably may also have a free carboxylate group content less than
45%, less than 15% of the total carboxylate group content.
Suitable alkali metal ions include sodium, potassium and mixtures
thereof. Suitable lower alkyl C.sub.1-3 amine salts include salts
of monomethyl amine, dimethyl amine, trimethyl amine, monoethyl
amine, diethyl amine, triethyl amine and mixtures thereof. Mixtures
of the ammonium salt and the lower alkyl amine salts may also be
used. The preferred non-metal salts are ammonium salts and salts
formed from amines having a molecular weight less than 60 and a
boiling point less than 20.degree.C.(760 mmHg).
The copolymer used in this invention can be produced by any one of
several known methods. The copolymer is generally produced by
copolymerizing styrene and an unsaturated carboxylic compound
selected from the group consisting of maleic anhydride maleic acid
and half esters of maleic acid in the presence of a solvent such as
toluene, and then neutralizing the resulting copolymer to form the
salts. The copolymer may be alternatively produced by just
copolymerizing styrene and the salts of the unsaturated carboxylic
compound. Half-esterification may be conducted after the styrene
and maleic anhydride or maleic acid are copolymerized. Suitable
alcohols for the esterification reaction include monohydric
aliphatic alcohols containing 1 - 20 carbon atoms and having a
straight or branched chain or an alicyclic ring. The preferred
alcohols have straight or branched chains and contain 4 - 8 carbon
atoms. The mole ratio of styrene to the unsaturated carboxylic
compound is generally 30 - 90 : 70 - 10, preferably 45 - 60 : 55 -
40.
The copolymer of this inventin may contain one or more additional
structural units. Suitable ethylenically unsaturated monomers as
the third monomer, or structural unit include monomers containing
carboxylic groups such as acrylic acid, methacrylic acid and
fumaric acid; vinyl monomers such as vinyl acetate, vinyl chloride
and .alpha.-olefins; acrylates and methacrylates such as methyl
acrylate, methyl methacrylate, butyl methacrylate, hexyl
methacrylate, octyl methacrylate and octyl acrylate; and other
specific acrylic monomers such as acrylamide and hydroxyethyl
acrylate. Among these monomers, the preferred are acrylates and
methacrylates having 4 - 12 carbon atoms. The third monomer may be
present in molar amounts less than 60% preferably less than 40% of
the total. When the third monomer contains a carboxylic group, the
group is included in the calculation of the carboxylate equivalent
and the percentage of carboxylate groups in a salt the copolymer of
the invention has a viscosity of at least 1000 cps. as a 40% by
weight aqueous solution at 30.degree.C.
The surface sizing composition of this invention may consist of the
abovementioned copolymer alone. However, the copolymer is generally
used with modifiers such as modified starches such as oxidized
starches and enzyme converted starches, and polyvinyl alcohols. The
weight ratio of the copolymer to the modifier may be 0.1 - 50 :
99.9 - 50. The copolymer may be also used with conventional sizing
agents and other modifiers such as rosins and petroleum resins.
The surface sizing composition of this invention may be applied to
paper sheets by any conventional method. Thus, the sizing
composition can be dissolved or dispersed in water to form a sizing
solution (1 - 20% by weight), and then the solution is applied to a
paper sheet by a size press, and the treated sheet is dried. The
amount of the copolymer deposited on the paper is 0.01 -
0.5g/m(solid).sup.2, preferably 0.05 - 0.15g/m(solid).sup.2. When a
modifier is used with the copolymer, the amount of sizing
composition deposited on the paper is 1 - 5g/m (solid).sup.2,
preferably 2 - 3g/m (solid).sup.2.
The surface sizing composition is used on various kinds of paper
bases such as paper which contains a filler, water-leaf paper and
soft-sized paper. The preferred paper is one which contains little
or no internal sizing composition.
The surface sizing composition of this invention has a good sizing
effect and good stability in the sizing solution. The sizing
solution containing the sizing composition of this invention,
therfore, does not form a scum even under long and severe operating
conditions in size presses.
Having generally described this invention, a futher understanding
can be obtained by reference to certain specific examples which are
provided herein for purposes of illustration only and are not
intended to be limiting unless otherwise specified.
In the examples, the viscosity was measured as a 40% by weight
aqueous solution at 30.degree.C., and the pH was measured as a 4%
by weight aqueous solution.
EXAMPLE 1
Into a four-necked, round-bottom 1000 c.c. flask equipped with an
agitator, a reflux condenser, a dropping funnel, a thermometer and
a tube for the introduction of nitrogen gas, were charged 230.8g of
methyl ethyl ketone, 1.0g of lauryl mercaptan, and 45.0g of maleic
anhydride. The mixture was heated at reflux with stirring under a
nitrogen atmosphere. Then, to the mixture was added a solution
which was obtained by dissolving 0.5g of
2,2'-azobisisobutyronitrile in 26.3g of styrene and 32.4g of methyl
methacrylate slowly over about 4 hours, and then the reaction
mixture was kept at a reflux for an additional 2 hours. The
resulting mixture was cooled to 60.degree.C by a water bath, and
then was neutralized with 37 g of a 10% by weight aqueous solution
of sodium hydroxide. The resulting neutralized solution was
distilled to remove methyl ethyl ketone, and then was treated with
50.3g of a 28% by weight aqueous solution of ammonium hydroxide
after being cooled to 60.degree.C. By this procedure was obtained a
40% by weight aqueous solution of the copolymer.
The resulting copolymer had a carboxylate equivalent of 109, a
viscosity of about 5000 cps., and a pH of 9.5. The copolymer had
10% of its total carboxylic groups in the form of the sodium salt
and 90% in the form of the ammonium salt.
EXAMPLE 2
Example 1 was repeated and a copolymer of the free carboxylic acid
was obtained. The resulting copolymer was esterified with 29.6g of
n-butyl alcohol to form a copolymer having a carboxylate equivalent
of 256. Then, the resulting copolymer was neutralized in the same
manner as described in Example 1 whereby a 40% by weight aqueous
solution of the copolymer was obtained which had 30% of the
carboxylate groups as the sodium salt and 70% of the carboxylate
groups as the ammonium salt. The copolymer had a viscosity of 8000
cps. and a pH of 9.4.
EXAMPLE 3
A copolymer was produced by the same method described in Example 1
using 178.2g of ethylene dichloride, 1.2g of lauryl mercaptan,
54.0g of maleic anhydride, 50.4g of styrene, 15.6g of n-butyl
acrylate and 0.6g of 2,2'-azobisisobutyronitrile. The solution was
neutralized whereby a 40% by weight aqueous solution of the
copolymer which had 15% of the carboxylate groups as the potassium
salt, 76% as the ammonium salt and the balance as the free
carboxylic acid was obtained. Furthermore, the resulting copolymer
had a carboxylic equivalent of 114, a viscosity of about 6,000 cps.
and a pH of 8.2.
EXAMPLE 4
A copolymer was produced by the same method described in Example 1
using 230.8g of toluene, 1.0g of lauryl mercaptan, 45.0g of maleic
anhydride 47.8g of styrene and 0.5g of 2,2'-azobisisobutyronitrile.
The solution was neutralized whereby a 40% weight aqueous solution
of the copolymer which had 20% of the carboxylate groups as the
sodium salt, 70% as the ammonium salt and the balance as the free
carboxylic acid was obtained. The copolymer had a carboxylic
equivalent of 101, a viscosity of about 9,000 cps. and a pH of
8.1.
EXAMPLE 5
Example 4 was repeated whereby a copolymer as the free acid was
obtained. The resulting copolymer was neutralized whereby a 40% by
weight aqueous solution of the copolymer which had 20% of the
carboxylate groups as the sodium salt, 70% as the monoethyl amine
salt and the balance as the free carboxylic acid was obtained. The
copolymer had a viscosity of 10,000 cps. and a pH of 9.4
EXAMPLE 6 (Test of Stability)
A stability test was conducted with each of the sizing solutions
prepared from the copolymer solutions produced in Examples 1 -
5.
An aqueous sizing solution (5,000 cc) was prepared which contained
0.8% by weight of each of the copolymers of the invention and 7.2%
by weight of an oxidized starch. For comparison, an aqueous sizing
solution was prepared using conventional sizing agents instead of
the copolymer of this invention. Each of the sizing solutions was
supplied to an inclined labo-size press by a handy pump. Outflow of
the solution waS recycled. The stability was determined by
observing the formation of scum every 30 minutes. Operational
conditions were as follows:
1. Press speed: 100 m/min.
2. Nip Pressure: 20 Kg/cm.
3. Operation Time: 8 hours
4. Temperature of the solution: Adjusted to 60.degree.C
5. pH of the solution: Aqueous alum solution 0.5% by weight was
added every 60 minutes, so that the pH was adjusted to 5.0, four
hours after starting.
The results of the stability tests are shown in TABLE 1.
TABLE 1
__________________________________________________________________________
No. Surface sizing Stability of the sizing solutions agents
__________________________________________________________________________
1. Example 1 No scum developed in the pressing operation for more
than 8 hours. 2. Example 2 " 3. Example 3 " 4. Example 4 No scum
developed in the pressing operation for more than 8 hours. 5.
Example 5 " 6. Rosin size Substantial development of scum in the
(Conventional) pressing operation after only 0.5 hour. 7. Petroleum
resin Substantial development of scum in the (Conventional)
pressing operation after 1.5 hours. 8. Styrene-maleic Substantial
developement of scum in the anhydride copolymer pressing operation
after 3.0 - 3.5 hours. (conventional)
__________________________________________________________________________
EXAMPLE 7 (Test of the sizing effects)
A test of the sizing effects was made on each of the copolymers
produced in Examples 1 - 5 in comparison to some conventional
sizing agents.
The operational conditions for sizing tests were as follows:
1. Base paper
Paper was produced by sheeting pulp L-BKP. The pulp had a degree of
beating of 420 contained clay (filler) and a fortified rosin
(internal sizing agent) at a pH of 4.5 (adjusted with alum). The
resulting paper had a weight of 60 - 62g/m.sup.2 with an ash
content of 13.0% and a rosin content of 0.09% by weight.
2. Surface sizing solution Oxidized starch 7.6 (% by weight) Each
sizing agent (active) 0.4 Water 92 TOTAL 100
3. Sizing opeation
The sizing operation was made with an inclined labo-size press at a
speed of 100m/min and a nip pressure of 10Kg/cm.
4. Resulting paper
The paper treated as mentioned above contained 0.1g/m.sup.2 of the
sizing agent and 2.0g/m.sup.2 of the oxidized starch.
The results of the sizing effect tests are shown in Table 2.
TABLE 2
__________________________________________________________________________
No. Surface sizing agent Sizing degree Writability IGT surface
(sec.) Strength (cm./sec.)
__________________________________________________________________________
1 Example 1 23.3 5 - 6 203 2 Example 2 21.1 5 - 6 184 3 Example 3
24.5 6 238 4 Example 4 23.0 5 - 6 208 5 Example 5 23.0 5 - 6 205 6
Rosin size (conventinal) 20.2 3 - 4 146 7 Petroleum resin 19.5 4
142 (Conventional) 8 Styrene-maleic anhydride copolymer
(Conventional) 21.5 5 - 6 193
__________________________________________________________________________
1. Sizing degree was determined by the Stockigt method (JIS
P-8122). 2. Writability was tested by the method of J. Tappi
Standard. No. 12. 3. IGT surface strength was determined by the
method of J. Tappi Standard T 499 Su-64, Surface strength of Paper
(IGT Tester).
Having now fully described the invention, it will be apparent to
one of ordinary skill in the art that many changes and
modifications can be made thereto without departing from the spirit
or scope of the invention as set forth herein.
* * * * *