DE1289405B - Paper sizing process - Google Patents

Description

a substituted cyclic dicarboxylic anhydride of the formula

, Cs

R —R '

consists in which R is a dimethylene or trimethylene radical and R 'is a hydrophobic alkyl, alkenyl, aralkyl or aralkenyl group with more than 5 carbon

and paperboard «fall sheet-like masses and shaped products made of natural cellulose material or a sizing agent which is of synthetic origin and similarly shaped
Products made from combinations of cellulose and
Non-cellulosic plastic materials, such as
Polyamide, polyester and polyacrylic resin fibers, and 15
mineral fibers such as asbestos and glass.

Paper and cardboard are often glued with all sorts of materials in order to maintain their strength
Water and aqueous solutions of any other kind too
raise. Such materials are called gluing 20
medium and introduces them during the actual papermaking process, this process being referred to as internal or machine sizing.
On the other hand, however, they can also mean carbon atoms on the surface of the finished web or sheet, the unsaturated ones being applied, and such a process carbon bonding in the larger proportion of alkenyl is called outer or surface sizing. or aralkenyl groups between the second and

You already have all sorts of water-repellent third carbon atoms away from the R bonded materials used as a sizing agent. For this purpose which carbon atom is located. Belong to the verb Resin, resin-wax mixtures, wax emulsions of this structure include the substituted amber ions, Ketene dimer emulsions, fluorocarbons, stone and glutaric anhydrides. In the case of the Fatty acid complexes of chromium or aluminum substituted glutaric anhydride can be the subchloride, long chain thermoplastic copolymers substituent R 'on the trimethylene radical, either on and thermosetting condensation resins. Although the one directly adjacent to the CC group or to the all these materials under certain conditions 35 central carbon atom, be bound, are effective, they are subject to one or the other

other restriction.

These restrictions include, among other things, that with many sizing agents that have been used to date Water resistance or resistance is insufficient for many uses. Also tolerated Experience has shown that many of them do not deal with the pigments, fillers or other additives, which are often added to the paper. Another disadvantage of the known sizing agents is furthermore that they require considerable thermosetting to develop the highest performance need.

According to the invention it has now been found that
by adding certain reagents to that at 5 °
Paper stock used in the manufacture of paper and cardboard can be used to achieve a paper which is characterized by an unusually high degree of water resistance and simultaneous resistance to acidic and alkaline
Solutions. Of particular importance is the fact that the application of this The type of actual use of the invented

new sizing agents are not limited to a specific sizing agent used according to the pH range, so that they can be largely varied according to the wishes of the practitioner. When treating neutral as well as acidic or alkaline, it is important to use a uniform chemical paper stock. In addition, the sizing agent can be dispersed within the sizing paper stock used according to the invention. It is therefore advisable to carry out the medium together with both alum and all the addition to the paper stock with careful and other pigments, fillers and other roughly vigorous agitation. A uniform used paper additives are applied. Distribution can also be achieved by the fact that 65 _m of the sizing agent is the paper stock in full , also for the purpose of achieving additional sizing- dispersed form, for example as an emulsion, effects combined with other sizing agents with the simultaneous addition of chemical effects may be dispersing. In addition, they adversely affect clogs.

means include, for example

Iso-octadecenylsuccinic anhydride, n-hexadecenyl succinic anhydride, dodecenyl succinic anhydride, Dodecyl succinic anhydride, decenyl succinic anhydride, octenyl succinic anhydride, Nonenylsuccinic anhydride, triisobutenylsuccinic anhydride, capryloxysuccinic anhydride, Heptylglutaric anhydride and benzyloxysuccinic anhydride.

Of the reagents of this type, acid anhydrides in which the radical R 'has more than 12 carbon atoms give contains, the best results. It should be noted that mixtures of these reagents can also be used used for the method according to the invention

3 4

The emulsifier incorporated according to the invention is preferably first dispersed in water

put sizing agent in association with one and only then the sizing agent under vigorous

Substance applied to which is added cationic stirring. If the latter is usually

Is nature or is to be ionized in such a way or is too dissociative as a solid wax, it has to be emulsified before emulsification

can ieren that one or more of them 5 are first melted,

or other positively charged units created a further improvement in water resistance

will. Experience has shown that these catheters are suitable for the papers produced according to the invention

ionic agents, as they are called from now on, can be achieved by

as a means to harden the sheets or molded products used according to the invention by

Better retain the sizing agent and the paper i ₀ 1 to 60 minutes at 80 to 150 C

Bring paper pulp fibers close. To the heated. Such post-curing is recommended before

Process according to the invention can be used in particular when sizing agents with hydrophobic

punching include alum, aluminum or - according to the earlier formula - R 'groups

chloride, long chain fatty amines, sodium aluminate, 12 or fewer carbon atoms applied

Polyacrylamide, chromium sulfate, animal glue, certain 15 will be. In and of itself, however, such a post-

thermosetting resins and polyamide polymers. For hardening for the successful implementation of the

the use as a cationic agent is particularly not necessary according to the method according to the invention,

Various cationic starches are of interest. The sizing agents used according to the invention

derivatives including primary, secondary, tertiary can be used for sizing paper made from cellulose fibers

and quaternary amine starch derivatives as well as other 20 of any kind as well as combinations of cellular

cationic N-substituted starch derivatives and catlose and non-cellulose fibers are used,

ionic sulfonium and phosphonium starch derivatives. In the paper sized according to the invention can

These derivatives can be made from all sorts of starch pigments and fillers of all kinds as well as others

varieties including maize, tapioca, potato, additives including alum and other sizing agents

Waxy maize, wheat and rice starch can be introduced.

will. In addition, they can either be used in their The sizing agents used according to the invention

original granular form or can be in amounts between about 0.05 to about 5%,

Gelatinized, cold-water-soluble products converted to dry paper weight in the finished product

be changing. related, are applied. Within this

Each of the aforementioned cationic agents depends on the amount actually used can the paper stock, e.g. B. the pulp, before, of course, mainly of the paper used, time with or after the addition of the sizing agent, the special working conditions and the be added. In order to achieve the best special purpose for which the division is the cationic agent however either paper is intended. For example, a in connection with or together with the sizing paper, which is characterized by particularly good water and medium added. The actual addition of kat- ink resistance should characterize the application ionic and from sizing agents to paper stock a higher sizing agent concentration than this can be used at any point in the paper-making problem for a paper During the process of converting the new paper peat, excessive sizing is not a prerequisite. the Similar considerations apply to a dry web or sheet 40 as well with respect to take place. The amount of cationic agent used in accordance with the invention is the amount of cationic agent, for example can therefore use the paper stock together with those used according to the invention Bütte, in Dutch, in hydropulper or in sizing agents. Under normal Stotfbütte can be added. However, conditions usually suffice from 0.5 to

To achieve good glueing, 45 2.0 parts by weight of the cationic agent are added to each

the sizing agents used according to the invention in 1 part of sizing agents. In those cases where those

the smallest possible particle size uniformly in particular, sizing agents used according to the invention

Dispersed paper stock. One way to do this is to use agents that contain hydrophobic groups

contain the sizing agent with 12 or fewer carbon atoms before it is added to the paper,

with the help of mechanical means, such as rapid 50, it is advisable to use these cationic agents in

to use stirrers, mechanical or ultrasonic homogenizations at the upper limit range,

by adding a suitable emulsifier, or by adding a suitable emulsion.

emulsify gators in water. If any possible embodiments of the invention are explained in more detail. In

borrowed, the earlier mentioned cat- they will refer to the details of parts contained in them

ionic agent used as an emulsifier, this 55 weight, unless otherwise specified.

Method is particularly effective when cat-. .

ionic starch derivatives can be used. To the example

non-cationic emulsifiers that can be used for emul- This example illustrates the use of the

Suitable sizing agents include those sizing agents used according to the invention in

Hydrocolloids like normal starches, non-cat- 60 form of aqueous emulsions, which with the help of a

ionic starch derivatives, dextrins, carboxymethyl tertiary amine starch derivative were produced, as well as

cellulose, gum arabic, gelatin and poly- their combined use with alum. the

vinyl alcohol and various wetting agents. If the resulting paper is water-resistant, it will be with

Use of such non-cationic emulsifiers compared to that of such paper that is only with

It is often desirable to add mixtures of reinforced resin and alum to the paper stock

if the emulsified sizing agent was still separately sized.

to add a cationic agent. The first was an aqueous emulsion of

Preparation of such emulsions using an isooctadecenyl succinic anhydride, below

IODBA for short, prepared by boiling 7.5 parts of the p'-diethylaminoethyl chloride hydrochloride ether of corn starch, the preparation of which is described in Example I of American Patent 2,813,093, in 85 parts of water. After boiling for 20 minutes, the dispersion of the cationic starch derivative was cooled and transferred to a high-speed stirrer, where 7.5 parts of IODBA were slowly added to it. After stirring for 5 minutes, the emulsion was diluted by adding an additional 900 parts. A final ten fold dilution was then effected and added to an aqueous slurry of bleached sulphate pulp having a consistency of 1.5% and a pH of about 8.5. From this material according to Tappi regulations sheets were formed which - based on dry matter - contained 1% each of cationic agents and sizing agents. The basis weight of the sheets was 89.5 g / m ² . Using the same procedure, comparable leaves containing different amounts of IODBA as well as those leaves containing IODBA in combination with different amounts of alum were produced. In all cases where alum was used, the pH of the aqueous pulp slurry was 5.0.

The water resistance of these sheets was compared with that of sheets obtained from comparable, but were made with a resin-alum mixture sized paper stock. For comparison The uranine dye and ink deep immersion tests were used to determine the waterfastness of these sheets. The former test was thus carried out.

that you put some uranine dye powder on top of a paper swatch and then that floated on distilled water. As soon as the water is absorbed into the paper, it becomes the dye moisturizes and is therefore sensitive to ultraviolet rays. The time measured in seconds that elapses until this ultraviolet sensitivity occurs, is therefore in direct proportion to the Water resistance of the paper, because of course a more water-resistant paper will dampen the on its Surface applied dye delayed accordingly longer.

The ink immersion test gives a qualitative comparison in which a sample of the test Paper is dipped in a 50:50 mixture of water and blue ink. After taking it out again the pattern is washed with water and the remaining color is measured colorimetrically evaluated. Thus, a more water-resistant pattern shows weaker staining than one little waterproof paper. An arbitrary color scale from 1 to 10 was used for this test, No. 1 has the lowest coloration or best water resistance and No. 10 the strongest coloration or indicated the lowest water resistance. This test also gives a qualitative visual indication for distributing the sizing agent in the paper.

The table below gives the data of the various sheets of paper compared and the results both tests again (IODBA = isooctadecenyl succinic anhydride).

sheet
■ No. additions No ⁰ ₀ . on fabric
based on dry weight Uranine dye test
(Time in seconds) Ink depth immersion test
(Color value) 1 Cationic corn starch
IODBA immediately 10 2 Cationic corn starch
IODBA
alum 1
1 105 3 3 Cationic corn starch
IODBA 1
1
2 118 2 4th Cationic corn starch
IODBA
alum OJ OJ 130 1 5 Cationic corn starch
IODBA 3
3
2 132 1 6th resin
alum 5
5 138 1 7th i
2 78 5

Example II

This example illustrates the use of octenyl succinic anhydride alone and in combination with alum as well as the post-hardening of the paper sheets glued with this short-chain derivative.

First of all, an octenylsuccinic anhydride emulsion was prepared according to the method described in Example I. The same cationic starch derivative also served as an emulsifier, but was pregelatinized beforehand, ie brought into cold-water-soluble form, by passing an aqueous slurry of the derivative over heated metal drums. As a result of its use in this pregelatinized form, it of course did not need to be boiled for the purpose of dispersion. The finished octenyl succinic anhydride emulsion was then stirred into a bleached sulfate pulp with the degree of freeness

500 and the consistency 1.5 ¹ Vo added, the slurry diluted to 0.5% consistency and some alum added, resulting in a pH of 5.5. The resulting paper sheets had a basis weight of 97.6 g / m 2 and contained - based on dry matter - 1% octenylsuccinic anhydride and cationic starch as well as 2 "/ o alum. They were ^{hardened for 1 hour at 105 °} C. For comparison purposes further test sheets from other polymer types produced in which a sizing agent on the one hand an aqueous IODBA emulsion example I was with the cationic starch derivative as prepared, and on the other hand uses a mixture of reinforced resin and alum. This comparison, ₅ papers were not The paper stock containing the IODBA had a pH of 8.0 The various test papers are listed below according to their composition and test result.

sheet
No. additions %, on fabric
dry weight
based Uranine
dye test
(Time
in seconds) 1 Cationic
Cornstarch 1.0 103
(1 hour
at 105 C.
hardened) Octenyl amber
stinic acid
anhydride 1.0 alum 2.0 2 Cationic
Cornstarch 1.0 152
(without
Hardening) IODBA 1.0 3 Reinforced
resin 1.0 94
(without
Hardening) alum 2.0

Example III

This example illustrates the use of normal corn starch as an emulsifier for IODBA.

According to the procedure given in Example I, an aqueous emulsion of the IODBA was prepared, however, normal corn starch is used as an emulsifier instead of the cationic starch derivative used there used. This emulsion was then bleached sulphate pulp with a stirring Grind of 5 (X) and a consistency of 1.5% were added, and this was followed by the addition of alum up to a pH of 5.5. The finished sheets contained - on cloth dry weight based - 1.0% IODBA and 1.0% corn starch and had a basis weight of 97.6 g m-. the The table below gives the composition and the uranine dye test values for this type of paper Compared to a paper made accordingly, but with reinforced resin and alum was glued.

IO

additions "," On fabric Uranine sheet dry weight dye test No. Cornstarch based (Time IODBA 1.0 in seconds) 1 Alum (to on 1.0 105 ■ the pH 5.5 a place) Reinforced resin 1.0 2 alum 94 2.0

30th

35

40

45

Example IV

This example describes the use of IODBA as a sizing agent for paper, the one Contains a fair amount of neutral pigment.

An aqueous IODBA emulsion prepared according to the procedure of Example I was added in portions Stir to a series of bleached sulfite pulp slurries with a degree of grinding of 440 and a consistency of 1.5% are added, which is also based on the dry weight of the fabric Contained 10% titanium dioxide, 10% calcium carbonate and 10% clay, respectively. The ones made from it Paper sheets contained - again based on the dry weight of the fabric - each 0.5% cationic Starch derivative and had a basis weight of 97.6 g / m2. From the table below are the Compositions and the water resistance values (according to uranine dye test) of these paper sheets im Can be read in comparison to papers which also contain pigment, but which are glued with reinforced resin and alum had been.

55

60

additions %, on fabric Uranine sheet dry weight dye test No. Cationic based (Time Cornstarch 0.5 in seconds) 1 IODBA 130 Titanium dioxide 0.5 Cationic 10.0 Cornstarch 0.5 2 IODBA 153 volume 0.5 Cationic 10.0 Cornstarch 0.5 3 IODBA 200 Calcium carbonate 0.5 Reinforced resin 10.0 alum 1.0 4th Titanium dioxide 2.0 96 10.0

Example V

This example describes the use of IODBA in an oily, non-emulsified form as an additive to the paper stock in combination with a kaiionic starch.

909 507-1495

Separate portions of the IODBA and the cationic corn starch derivative described in Example I were added simultaneously with stirring to a stock of 73% wood pulp and 27% bleached sulfite pulp with a freeness of 350 and a consistency of 1.5%. The paper sheets produced therefrom contained 1% IODBA and cationic starch each, based on the dry material weight, and had a basis weight of 53.7 g / m ² . The table below shows the compositions and the water resistance values (according to the uranine dye test) of these paper sheets in comparison with papers which, however, had been sized with reinforced resin and alum.

15th

additions %, on fabric Uranine sheet dry weight dye test No. Cationic based (Time Cornstarch 1.0 in seconds) 1 IODBA Reinforced resin 1.0 alum 1.0 104 2 2.0 80

Example VI

This example reports the use of IODBA in emulsion form, with each Emulsions with a cationic amine derivative of a different type of starch as a sizing agent were manufactured. In addition, the influence of post-curing on the water resistance is shown.

The various emulsifiers used were each a tertiary amine starch derivative, namely a / i-diethylaminoethyl chloride hydrochloride starch ether the type of formation described in Example I of American Patent 2,813,093, however Instead of the maize starch used there, another type of starch, namely a waxy maize starch, Tapioca starch, a potato starch, brought to so-called 85 fluidity through acid treatment Waxy maize starch and a maize starch brought to fluidity by acid treatment are used became.

Each of these individual tertiary amine starches was then used as an emulsifier for the production of the individual aqueous IODBA emulsions used. These were then individually bleached in the vat Sulphate pulp batches with a freeness of 500 and a consistency of 0.5% were added. The paper sheets obtained from the individual batches contained - on dry fabric weight based on - 1% each IODBA and respective tertiary amine starch variety. They were tested for water resistance according to the uranine dye test described in Example I. checked out. The same thing happened with other paper samples, but they did so before the uranine dye test post-cure for 1 hour at 105 ° C. Composition and water resistance of the various paper samples are shown in the table below.

sheet
No. additions %, on fabric
dry weight
based Uraninfa
(Time in p
immediately substance test
customers)
hardened 1 Waxy maize tertiary amine
IODBA 1.0
1.0 102 102 2 Tapioca tertiary amine
IODBA 1.0
1.0 110 118 3 Potato tertiary amine
IODBA 1.0
1.0 112 118 4th Acid converter Waxy maize tertiary amine
IODBA 1.0
1.0 83 93 5 Acid converter Tertiary amine starch
IODBA 1.0
1.0 95 109

Example VII

This example reports on the use of several sizing agents used according to the invention, namely, n-hexadecenyl succinic anhydride, dodecenyl succinic anhydride, dodecyl succinic anhydride and a mixture of isoalkenyl succinic anhydrides, their alkenyl groups Contained 18 to 22 carbon atoms.

Each of these sizing agents was made according to the procedure described in Example I and with the same The cationic starch derivative described there prepared an aqueous emulsion. From these emulsion approaches became those with the mixed isoalkenyl succinic anhydrides and those with the n-hexadecenylsuccinic anhydride each in the hydro bath bleached sulphate pulp with a consistency of 1.5% and a degree of freeness of 510 added, while the other two approaches, with dodecenyl or dodecyl succinic anhydride each Sulphite pulp bleached in the pulp with a consistency of 0.5% and a degree of grinding of 500 were added. The paper sheets obtained therefrom contained - based on dry fabric weight - 1% each of the corresponding sizing agent and 1% cationic starch. From the subsequent The table shows the compositions and the water resistance values (according to the uranine dye test) of these Paper sheets readable in comparison to papers, but which have been glued with reinforced resin and alum was.

additions %> on fabric Uranine sheet track weight dye test No. Mixture of iso- based (Time alkenyl amber 1.0 in seconds) 1 acid anhydrides 120 Cationic Cornstarch 1.0 n-hexadecenyl succinic acid 1.0 2 anhydride 118 Cationic Cornstarch 1.0 Dodecenyl amber stinic acid 1.0 3 anhydride 110 Cationic Cornstarch 1.0 Dodecy 1 amber acid anhydride 1.0 4th Cationic 105 Cornstarch 1.0 Reinforced resin alum 1.0 5 2.0 98

Example VIII

This example shows the excellent resistance of a paper sized according to the invention to acidic and alkaline solutions compared to papers made with mixtures of reinforced resin and alum were glued.

Following the procedure of Example I and using the emulsifier used there

In the case of cationic tertiary amine starch, an aqueous emulsion of IODBA was prepared and added, with stirring, to a bleached sulphate pulp with a degree of freeness of 500 and a consistency of 0.5%. The paper sheets produced therefrom contained 0.5 "/ o each of IODBA and cationic starch and a basis weight of 89.5 g / m ² .

These paper sheets were tested for uranine dye tested for fluid resistance, but the test was modified in such a way that the paper swatches covered with dye powder in one case to an aqueous 10 percent by weight Lactic acid solution and in the other case placed on a 10 weight percent aqueous sodium hydroxide solution became. In the same way, paper samples made with a mixture of reinforced resin were tested and alum were glued. The compositions of the individual paper samples and their strengths against acidic or alkaline solutions are given below.

sheet

additions

"y" based on dry weight uranine dye test
(Time in seconds)

Lactic acid

Caustic soda

Cationic corn starch
IODBA

Reinforced resin
alum

0.5
0.5

1.0
2.0

106

> 200

25th

It was pointed out earlier in the description that all possible wetting agents suitable as emulsifiers for the sizing agents used according to the invention. These include among other things

Polyoxyethylene sorbitan trioleate,
Polyoxyethylene sorbitol hexaoleate,

Polyoxyethylene sorbitol laurate and
Polyoxyethylene sorbitol oleate laurate.

In summary, it can be stated that the invention provides the practitioner with new sizing agents which are effective under all possible conditions and produce paper products which are distinguished by exceptionally high water resistance.

Claims (3)

Patent claims: 1. Process for paper sizing, thereby characterized in that one is in the wet paper stock before its final conversion a sizing agent is intimately dispersed into the dry paper web, consisting of a substituted cyclic dicarboxylic anhydride of the formula 60 O R-R ' V / Il
ο consists, in which R is a dimethylene or trimethylene radical and R 'is a hydrophobic alkyl, alkenyl, aralkyl or aralkenyl group with more than 5 carbon atoms, the unsaturated carbon-carbon bond in the larger proportion of the alkenyl or aralkenyl groups between the second and third carbon atom is remote from the carbon atom bonded to R. 2. The method according to claim 1, characterized in that one is in the wet paper stock before its final conversion into the dry paper web is also a cationic agent intimately dispersed. 3. The method according to claim 1 or 2, characterized in that the sizing agent in Applying the form of an emulsion.