DE2547700A1 - PAPER CONTAINING ALAUN AND PROCESS FOR ITS MANUFACTURING - Google Patents

Description

D1PL.-PHYS. F. FINALLY

PATENT ADVOCATE 09 flkt '^ ¹

UNTERPFAFFENHOFEN ^ '

P.O. BOX

N-3818 Dr.K./zb

National Starch and Chemical Corporation, Bridgewater,

N. Y., USA

Paper containing alum and process for its manufacture

The invention relates to a method for producing paper and the improved paper obtained thereby. In particular, the invention provides an additive that is incorporated into the paper pulp during papermaking can be incorporated, whereby the pigment retention is improved and the paper a greater strength as well as other desirable properties can be imparted.

According to the invention one sees the addition of new starch products to the paper pulp, which represent new starch derivatives, the controlled proportions of katiogenic or cationic substituent groups and 'SuIfοsuccinatgruppen contain.

The term "paper ¹¹ " as used herein is intended to denote sheet-like masses and shaped products made of fibrous

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Cellulosic like materials have been made which are derived from natural sources as well as from synthetic products such as polyamides, polyesters and polyacrylic resins as well as mineral fibers such as asbestos and glass. This term is intended to include paper made from combinations of cellulosic and synthetic materials have been manufactured. The broad term paper should naturally also include cardboard.

It is already known to form the pulp or the pulp during the papermaking process and prior to sheet formation to give different materials such as starch. The purpose of these additives is mainly is to promote fiber bonding and facilitate the production of strong paper.

It is also known in the case of papers containing added pigments such as titanium dioxide, to add materials to the pulp or pulp for the specific purpose, a greater proportion of such Retain papers in the paper (instead of letting them run off with the water removed as the sheets form will). Such additives are often called "pigment retention agents" designated.

One of the serious problems that has hitherto occurred in papermaking has been the appearance that the Additives that have been used to bind and strengthen the paper have an insufficient effect of improving it had pigment retention or, in many cases, they were actually that retained by the paper Decreased amount of pigment. Likewise, those additives that were most effective as pigment retention agents had no effect on the finished paper sheet

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to solidify, and in some cases they even reduced it considerably.

The aminoalkyl starch ethers described in US Pat. No. 2,813,093 which are used in the papermaking process according to US Pat US Pat. No. 2,935,436 did have certain improvements both in terms of paper strength and pigment retention. Nevertheless one still has looked for major improvements, with particular effort being made to provide an additive at a low pH range in the presence of aluminum salt regardless of the hardness of the water, which is used in the pulp and for cooking the starch, is effective.

It has been suggested to use starch phosphates as pigment retention agents to use. Their effectiveness is on paper stocks that have low to moderate alum concentrations contained, have been recognizable.

At higher alum concentrations, however, the effectiveness of starch phosphates decreases, which has not yet been recognized Reasons. This phenomenon is possibly due to the fact that the phosphate groups act as weak acids which are incapable of achieving the desired pigment retention and increased paper strength in the presence of alum concentrations which are greater than 4% by weight in the dry pulp. Consequently are starch phosphates (e.g. di- and trialkylaminoalkyl starch phosphates) as well as other prior art anionic starch derivatives that operate at low concentrations of alum are effective, in comparison to the new starch products according to the invention, worse at higher alum concentrations.

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At low alum concentrations, certain improvements " pigment retention behavior can be obtained by adding carboxyl groups in starch amine alkyl ethers or native starches, for example carboxymethyl groups or half ester groups (for example succinate groups or maleate groups) introduces.

In this case, too, one has to search for further improvements with the particular aim of finding an additive that would work at higher alum concentrations like her often in the paper industry, especially in connection with the increased use of recycled paper present, is effective.

The object of the invention is therefore to provide new starch products which can be used for the production of paper with high alum acidity are suitable.

An additive is also to be made available which is suitable for papermaking and which is suitable for the pulp or mass can be added at any point during the papermaking process prior to sheet formation and which ultimately is able to improve both pigment retention and strength of the paper.

It has now been found that the addition of the new starch derivative described below to the pulp can be used with any Stage before the formation of the paper sheet leads to a significant improvement in pigment retention along with an associated increase in paper strength at alum concentrations of more than 4% by weight on the dry pulp.

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254770Q

The new additives according to the invention are starch derivatives of non-gelatinized starch bases having a water flowability between about 4 and about 40, the starch derivatives being a controlled amount of cationogenic or cationic aminoalkyl ether groups or quaternary Contain ammonium ether groups along with a controlled amount of sulfosuccinate groups. In addition to the nitrogen / cationic groups and sulfosuccinate groups mentioned above can be the Additives also include phosphate groups as described below contain hydroxypropyl groups, acetate groups or other substituent groups in amounts which allow the granular starch character and an increase in solubility.

As cationogenic or cationic substituents in the starch additives according to the invention, tertiary amine ether or quaternary ammonium ether groups are preferred. However, others are also cationogenic or cationic Suitable for groups such as B. primary and secondary amine groups, sulfonium and phosphonium groups, which by ether or Ester bonds are attached.

The preparation of the aminoalkyl ethers of starch in which the starch derivative containing tertiary amine groups is described, for example, in US Pat. No. 2,813,093. In the US-PSn 2,989,520 and 3,077,469 describe sulfonium and phosphonium derivatives of starch.

It is known that quaternary ammonium groups are present in the starch molecule by appropriate treatment of the tertiary aminoalkyl ether of starch can be introduced as it for example, in U.S. Patent No. 2,813,093. It is

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also known that quaternary groups can be introduced directly into the starch molecule, for example by treatment with the reaction product of an epihalohydrin and a tertiary amine or tertiary amine salt.

As already stated, the starch derivatives must be used as additives for the paper pulp in the case of the invention Process to be apt to contain sulfosuccinate ester groups. It should be mentioned that for the purposes of present invention the sulfosuccination of starch, d. H. the chemical introduction of sulfosuccinate groups, to the anhydroglucose units must be carried out after the starch with the nitrogenous cationogenic or cationic groups has been modified and preferably after it has been converted.

There are already various methods of sulfosuccination in the art the starch base known. For example, in U.S. Patent No. 2,825,727, a method of treating is ethylenic unsaturated starch derivatives, prepared by the methods of US Pat. Nos. 2,461,139 and 2,668,156 with bisulfite, described.

The starch bases which are suitable for the process according to the invention must be in intact grain form and they must have a water flowability of at least 4, but not more than 40, or have been converted in this way, that they have such values. Suitable starch bases therefore include those in the non-gelatinized form a, which can be of any vegetable origin, for example from maize, rice, cassava, sago, waxy maize, Sorghum, potato, sweet potato, wheat, high amylose corn and the like. The selected starch can be used in

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their fluidity or low-boiling form can be converted at any stage prior to sulfosuccination, each being suitable degradation method can be used, for example the thermal treatment of granular starch in the presence of * 3N sodium phosphate with amylase or the mild oxidative "Conversion or the mild acidic hydrolysis or controlled enzyme conversion. Because therefore the necessary conversion the starch to a water flowability within the prescribed range before or after the modification the cationic groups can be carried out, the selection of the order before the sulfosuccination is carried out Leave to practitioners. It was also found that the phosphate ester groups as found in potato starch be, or the introduction of such groups in Maisbzw. Grain starch through heat reaction with phosphate salts makes the starch suitable for the introduction of the sulfosuccinate groups without conversion. The degree of substitution (S. G.) The phosphate groups can range from 0.003 to 0.01 extend.

It has been found that starch derivatives which are used for the inventive Processes are suitable, should be substituted with cationogenic / cationic groups to the extent that that their degree of substitution (S. G.), d. H. the average number of cationogenic / cationic groups per anhydroglucose units of the starch molecule differs from extends from about 0.005 to 1.50, is generally at least 0.01, and preferably from about 0.02 to about 0.04 extends. In the case of higher S.G. ranges, it is necessary to protect the grain structure using known measures.

All of the above types of substituent groups

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can be used separately or in combination with other suitable nitrogen-containing groups or with sulfonium or phosphonium groups can be used as long as the total S.G. value does not go beyond about 1.50.

The amount of sulfosuccinate ester groups chemically bonded to the starch molecule, and particularly to the anhydroglucose moiety, is important because it affects pigment retention in the presence of alum concentrations greater than about 4 % . While the presence of very small amounts of the sulfosuccinate ester groups shows improvements (e.g. 0.008 moles per mole of anhydroglucose units), amounts of 0.02 or more are preferred.

Because the aim of this invention is not in a balanced behavior at different pH values but in an improved behavior in the presence of high alum concentrations the ratio of the anionic groups to the cationogenic or cationic groups is of lesser importance. However, the presence of cationogenic or cationic groups significantly improves retention and the strength at low concentrations of alum.

As mentioned above, it is also possible to use starch derivatives in the process according to the invention, which, in addition to the required cationogenic / cationic and sulfosuccinate groups, also contain other substituent groups .

The technique of phosphorylation of a starch base is known. For example, U.S. Patents 2,824,870; 2,884,412 and 2,961,440 different phosphorylation techniques, essentially consisting of:

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Starch impregnated with a phosphate salt of an alkali metal is converted into heat within a prescribed pH range. For the purposes of the invention are the phosphorylations are limited to reactions of starch with any phosphorylating agent which has orthophosphate monoester groups, d. H. Monostarch phosphates.

A representative method for carrying out a suitable phosphorylation corresponds, for example, to a method as described in U.S. Patent 3,459,632.

The preparation of the phosphonium and sulfonium starch derivatives is described, for example, in U.S. Patents 3,077,469 and 2,989,520 described.

Naturally, various other optional cationogenic or cationic substituents can be used in a similar manner be added to a common anhydroglucose unit, it being repeated at this point that it for the implementation of the process according to the invention it is not only essential that the starch base has a water flowability between 4 and 40 is converted, or naturally contains phosphate groups, but that also the synergistic Combination of the aminoalkyl ethers or quaternaries Ammonium groups and the sulfosuccinate groups within must lie within the prescribed range.

Other suitable cationogenic or cationic starch derivatives are known to the practitioner, and at this point again it is repeated that in the process according to the invention all starch derivatives can be used which have a cationic (i.e. a positively electrically charged) portion in the starch molecule.

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The starch derivatives described herein are mainly used as Dutch additives, although their addition occurs at any point in the papermaking process the final conversion of the wet pulp to a dry web or sheet. So the products can for example be added to the pulp while it is in the head box, the the Hydropulpeinricht or the bulk chest is located.

The pigment retention and firming agents according to the invention can naturally be used effectively as additives for pulps made from any type of cellulose fiber, Synthetic fibers or combinations thereof have been made. Examples of cellulosic materials used are fibers made from bleached and unbleached sulfate (Kraft), bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite, semi-chemical, chemically ground wood, ground wood and any combination of such fibers. If so desired Viscose rayon or regenerated cellulose fibers can also be used.

Any desired, inert mineral fillers are given. Such materials are for example clay, titanium dioxide, talc, Calcium carbonate, calcium sulfate and diatomaceous earth. Rosin or synthetic internal sizing agents can be used if desired also be present.

With regard to the proportionate amount of the starch derivative to be incorporated into the paper pulp, it has been found that this amount can vary depending on the particular pulp used. In general, about 0.05 to 2.0 % starch is preferred

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derivative based on the dry weight of the pulp to be used. Within this preferred range, the exact amount used will depend on the type of pulp used, the specific operating conditions and the particular end use of the paper. The use of amounts of the starch derivative in excess of 2% based on the dry weight of the pulp, while not precluded, is usually unnecessary in order to obtain the desired improvements. When added in the correct concentration, the starch derivatives serve to increase pigment retention and paper strength, while at the same time providing the finished sheet with improved resistance to sagging, staining and scuffing.

The starch derivatives used in the process according to the invention contain cationic aminoalkyl ether or quaternary ammonium groups and sulfosuccinate ester groups in carefully selected proportions, whereby a combination of charges is obtained, which alternatively at varying application conditions, for example with varying alum concentrations or water hardness, come into play comes. Furthermore, which is surprising, the products according to the invention result from the interaction of the sulfo-succinate, cationogenic and cationic groups over a wide range of water hardness and alum concentration a well-balanced behavior. They show behavior maxima with regard to pigment retention and paper strength at high alum concentrations, which so far could not be obtained with starch products, which are either cationogenic or cationic or anionic groups alone or in combination with each other according to the prior art have received. This surprising synergistic effect is what the additives according to the invention imitate the products

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significantly superior to the prior art over a wide range of papermaking operating conditions operating in the presence of more than 4 % by weight alum in the dry pulp.

The invention is illustrated in the examples. In the absence of any information to the contrary, all parts are based on weight based.

example 1

This example describes the preparation of a typical alkylamine, phosphate and sulfosuccinate starch derivative which is suitable for the invention.

The procedure of Example 1 of U.S. Patent 3,459,632 was followed to modify a quantity of granular corn starch containing tertiary amine and phosphate groups. The resulting starch derivatives had about 0.3% by weight nitrogen and about 0.08 % phosphorus on the same basis. Note that because the starch base was phosphorylated, that is, modified with phosphate groups, its conversion was not required. The SG value of the phosphate groups was about 0.008.

Part 1: For the chemical introduction of sulfosuccinates into one Part of the modified starch described above was about 100 parts of the modified starch in about 125 parts of tap water suspended. The suspension was stirred and the pH of the resulting slurry became 7.2 adjusted by adding dilute sodium hydroxide solution and kept at this value while 1 part of maleic anhydride was added in small portions. The mixture was then stirred for about 1 hour

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left to react for a long time to ensure complete esterification. About 6 parts of sodium metabisulfite were then added slowly added to the reaction vessel. This mixture was stirred and at ambient temperature for about Reacted for 16 hours. After completion of the reaction, the pH of the system was adjusted by adding hydrochloric acid set to 5.5. The reaction product was then collected by filtration, essentially with tap water Washed salt-free and dried. The resulting product has an S.G. value of about 0.028 in terms of tertiary Amine groups and an S.G. value of about 0.01 with respect to the sulfosuccinate groups. Part of the dried The starch product was then used as an additive in the manufacture of paper and subsequently as below indicated, examined for pigment retention properties.

Part 2: Portions of the starch derivative described above were added to a bleached sulfite pulp containing varying amounts of paper alum, ie aluminum sulfate. The parts of the starch derivative were added to the papermaking pulp at a concentration of 0.25 % based on the weight of the dry pulp. The three pulps contained 4.0, 11.0 and 15.0 weight percent alum based on the total system. In each case, the pigment retention value of the test paper pulp and that of a blank sample and a control sample were determined, paper sheets were first produced on a Williams standard sheet form and these were then reduced to the percentage retained by the TAPPI standard method T 4i3-ts-66 Titanium dioxide (TiO ₂ ) were investigated. The blind sample consisted only of the papermaking pulp without any additive. The control sample consisted of a hand-made

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common pulp with a tertiary amine phosphate starch derivative, The test results obtained are summarized below.

Ti0 ₂ retention in the presence of the following amounts of alum, % +

4.0

Tested material

Test sample

Additive

tertiary amine phosphate sulfο succinate starch

Blind pin up 43

Control tertiary amine phosphate 72 sample

11.0

73

37 56

15.0

. 72

42 52

⁺ based on weight percent of dry pulp.

The above values clearly show the improved pigment retention, which can be obtained by the new starch products of the invention.

Example 2

This example further describes the increased pigment retention efficacy of the starch derivatives of the invention using a relatively larger amount of sulfosuccinate groups.

The procedure steps of Part 1 of Example 1 were repeated with the exception that two parts of maleic anhydride were used to esterify the modified corn starch prior to sulfonation. The resulting starch derivatives had S * G. values of 0.026 and 0.03 for the tertiary Amino groups or the sulfosuccinate groups. When testing

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of a portion of this starch product according to Part 2 of Example 1, this product showed pigment retention values that were comparable to those of the test sample of this example.

Example 3

This example describes the increased pigment retention efficiency the starch derivative according to the invention, with a relatively larger amount of the succinating agent using a slightly smaller amount of the sulfonating agent was used.

The process steps of Part 1 of Example 1 were repeated with the exception that a tertiary aminophosphate potato starch was further modified with two parts maleic anhydride and four parts sodium metabisulfite. The resulting product had SG values of 0.03 and 0.02, respectively, for the tertiary amino groups and the sulfosuccinate groups. When tested by the method of Part 2 of Example 1, this derivative exhibited pigment retention values in the presence of varying higher levels of alum from 79% »75 % and 76 %, respectively.

Example 4

This example describes the preparation of a sulfosuccinate derivative a cyclic tertiary amine starch for use as a pigment retention additive for a papermaking pulp.

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For the preparation of the additive described above were 100 parts of potato starch slowly mixed in 125 parts of water. The suspension thus formed was then with 1 part Betachloräthylpiperidin-HCl in the presence of 0.5 Parts of calcium oxide reacted over a period of 16 hours at ambient temperature. Then "the pH the resulting slurry was adjusted to 3.0 with hydrochloric acid. The reaction product was then filtered off, Washed salt-free and then with 2 parts of maleic anhydride and 4 parts of sodium metabisulfite according to Part 1 of the Example 1 implemented, whereby the tertiary aminosulfosuccinate starch derivatives were obtained. The respective pigment retention values this derivative, determined according to Part 1 of Example 1, were 80, 76 and 76. The product had S.G. values of 0.01 and 0.02 for the tertiary amino groups and the sulfosuccinate groups, respectively. These results show that a starch derivative, the starch base containing naturally occurring phosphorus, as a paper additive according to FIG Invention can be used. These results also indicate that when a starch base is used, the conversion step can be omitted prior to sulfosuccination.

Example 5

This example describes the preparation of a quaternary ammonium sulfosuccinate starch derivative useful in the invention suitable is.

To produce the starch derivative described above, 100 parts of corn starch slowly stirred into 130 parts of tap water which contained 4 parts of calcium hydroxide. the Corn starch had a water flowability of about 8. Die suspension formed in this way was then mixed with 3 parts

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len trimethyl-S-hydroxy ^ -chloropropyl-ammonium chloride under Stir and reacted at ambient temperature for about 16 hours. The pH of the resulting The slurry was then adjusted to 3.0 with hydrochloric acid. The reaction product was then filtered off, im Washed essentially free of salt and then suspended in about 140 parts of water. Two parts maleic anhydride and then 5 parts of metabisulfite were treated with the quaternary amine-modified starch of the suspension according to Part 1 of the Example 1 implemented. The modified starch product had an S.G. value for quaternary ammonium groups of 0.01 and an S.G. value for sulfosuecinate groups of 0.03. Then 3 equal parts of the quaternary ammonium sulfosuccinate starch derivative prepared in this way each added to a papermaking pulp slurry containing varying amounts of alum. The three pulps used contained 4.0, 11.0 and 15.0% by weight of alum, based on the total weight of the alum respective mixture. The parts of the starch derivative were each based at a concentration of 0.25% by weight based on the weight of the dry pulp. The pigment retention value of the individual paper pulps obtained from the the above three test pulps were obtained, and those of a blank and a commercially available one Control samples were determined according to Part 2 of Example 1. The papermaking pulp in the case of the blanks of the Control sample was as in Part 2 of Example 1. Below are the test results obtained.

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13th 17th 73 8th 50 45 41 64

Ti0 ₂ -R.etention in the presence

Tested ^{the fol} g ^end Alaunmengen,% +

Material 4.0 11.0 15.0

Test sample blank sample control sample

⁺ based on weight percent of dry pulp.

The results presented above clearly show that the quaternary ammonium sulfosuccinate starch derivative prepared according to the invention are particularly well suited for the production of paper if the papermaking composition is a Contains pulp which is relatively high in alum content.

Example 6

This example shows the increased pigment retention efficiency of the starch derivatives according to the invention using an alkylaminophosphate sulfosuccinate starch derivative to which the starch base has been converted through varied acid treatments.

For the preparation of each of the four test samples a tertiary Aminophosphatmaisstärke by the method of Example 1 was U.S. Patent No. 3,459,632 prepared. It was converted to WF (water flowability) values of about 8 to 35 by treatment with varying amounts of hydrochloric acid and then further modified with sulfosuccinate groups. The acid conversions were carried out at 52.5 ⁰ C over a period of about 16 hours. After each reaction was complete, the resulting mixture was neutralized by adding dilute NaOH and the tertiary aminophosphate starch was filtered off and then washed. Here-

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About 150 parts of each product were further increased by treatment with 2 parts maleic anhydride and 4 parts sodium metaMsulfite modified. The S.G. value for the tertiary amine groups and for the sulfosuccinate groups was 0.03 and 0.02, respectively. The pigment retention values for the four test samples and those of the blank and the three varied controls were determined in accordance with Part 2 of Example 1. The varying amounts of hydrochloric acid used to convert the starch varied Amounts of alum used in the pulp and the test values obtained with the various materials are shown in the table below.

Tested HCl TiOp retention in GeMaterial (Parts) in the presence of the consequences

the amounts of alum, % +

4.0 11.0

Sample A Tertiary aminophosphate sulfosuecinate starch 0.25 79 75

sample B. (Same product,
as in sample A ver
turns) 0, 5 81 90 sample C. Il 0, 75 73 75 sample D. Il 1, 0 74 76 Control Tertiary amine starch « 56 46

sample # 1

Control Tertiary Amine Phosphorus

sample # 2 phat starch, 79 52

Control tertiary amine sulfo-

sample no.3 succinate product

an unconverted starch - 60 59

Blank 44 45

+ based on weight percent of dry pulp.

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The values compiled above clearly show that it is the improved pigment retention aimed at according to the invention To obtain, it is essential that the starch base is both converted and with the nitrogen-containing groups and the sulfosuecinate groups is modified.

Example 7

This example shows the suitability of a starch derivative according to the invention as an additive for papermaking pulp, wherein the starch base of the derivative has been converted prior to modification. This example illustrates continues to be the essential nature of the conversion step in the manufacture of the papermaking additives of the invention.

An additive test sample was prepared by treating an amount of corn starch with 0.5% HCl to a WF of about 10 and then diethylaminoethylating the starch according to the procedure of Attachment A of Example 1 of U.S. Patent 3,459 and by then further modifying the starch with sulfosuccinate groups according to the method of Annex 1 of Example 1. The resulting starch product had a DS for the diethylaminoethyl groups of 0.03 and an DS for the sulfosuccinate groups of about 0.02. This additive test sample and four varied control samples were added to bleached pulp at concentrations of 0.25 % based on the weight of the dry pulp. For each additive and a blank sample, the pigment retention values were determined with varied alum values according to Part 2 of Example 1. The identification of the control samples and their respective descriptions are as follows:

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Control sample No. 1: corn starch, modified with sulfosuccinate

groups (S.G. value of about 0.02) the method of Part 1 of Example 1;

Control sample # 2:

Corn starch modified with diethylaminoethyl groups (S.G. value of about 0.03) according to the method of part A of the example. 1 of U.S. Patent 3,459,632;

Control sample No. 3

Control sample No. 4;

Corn starch modified with both diethylaminoethyl groups (S.G. value of about 0.03) and sulfosuccinate groups (S.G. value of about 0.02) according to the methods described above;

Corn starch that is first acid converted in the same way as the starch base of the test sample and then with diethylaminoethyl groups (S.G. value of about 0.03) according to the procedure of the part IA of U.S. Patent 3,459,632.

The following table shows the results of the pigment retention determinations the additive test sample described above, the four control additives, and the blank.

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Ti0 ₂ retention in the presence

Tested No. 1 of the following amounts of alum, % + 11.0 material η 2 71 Test sample η 3 59 Control sample Il 4th 46 η 59 ti 46 η 4.0 69 62 56 60 52

Blank sample (pulp without additives)

⁺ based on weight percent of dry pulp.

Those for the test sample and control sample No. 3 in the The values given in the table above clearly show the exceptionally good pigment retention behavior of the invention Starch derivatives, the starch base having been converted before esterification.

Example 8

This example further describes the improved pigment retention properties an aminoalkylate sulfosuccinate starch derivative in which the starch base prior to esterification acid converted with a varied amount of maleic anhydride.

To prepare the three additive test samples, a Amount of tertiary amine corn starch according to Example 1 of US Pat 3,459,632 and then converted to a WF of about 8 by treatment with 0.5 part HCl.

The resulting converted starch product was then divided into three equal parts. The individual parts of the

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The starch product was made with a varied amount of maleic anhydride esterified and then sulfonated by reaction with four parts of sodium metabisulfite. The acid conversions were carried out at 52.5 ° C over a period of 16 hours. The individual obtained in this way tertiary amino sulfosuccinate starch derivatives were filtered off, washed and dried. These additive test samples, two commercially available starch additives for paper production and a blank sample were used in accordance with Part 2 of Example 1 examined for the pigment retention properties. The following table shows the amounts of maleic anhydride, those used to prepare the individual additive test samples as well as the corresponding ratio of tertiary Amino groups put together to form sulfosuccinate groups. These Table also contains the descriptions for two control samples.

S.G. value

Tested
material

Sample E.

Sample F.

Additive

SG value TiOp retention of the sulfoder- in the presence of the tertiary
Amino groups

succinate groups

of the following amounts of alum, % + 4.0 11.0

Control sample No. 1

Control sample No. 2

Blank sample

Tertiary amine 0.01 sulfosuccinate starch

(Same product as used in sample E)

Tertiary aminoalkyl ethers of starch (manufactured according to the Author d. Example 1 d. U.S. Patent 2813093

Phosphorylated tert. Aminoalkyl ethers of starch (produced according to the version of Example 1 of US-PS 3 459 632 (S. G. value of approx

° '° ³⁾ 609818/1028

0.03

0.03

75 74

76 74

55

56

43

The values compiled above clearly show the improved Pigment retention that can be obtained using the novel products of the invention. They continue to show that the extremely high percentage of pigment in the presence of larger amounts of alum is only continuously maintained when the additive test samples were used.

Example 9

This example describes the suitability of low-boiling starches for the production of the new paper additives Starch base according to the invention.

To prepare the two additive test samples, the Process steps of Example 7 repeated, with the exception that in each case a low-boiling waxy maize starch with a particular water flowability (WF) value was used. Each of the resulting starch derivatives had a tertiary amine S.G. of about 0.03 and an S.G. value of the sulfosuccinate groups of about 0.03. The two additive test samples and one blank were used tested according to part 2 of example 1. The WF values of the waxy maize starch used for production are given below the additives were used. The corresponding pigment retention values are also given.

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TiOp retention in the presence of the following amounts of alum, °

Material WF 4.0 parts 11.0 parts

_. . . of the following amounts of alum, %

Tested

Test sample H 24 72 79

Test sample I 36 68 76

Blank sample - 43 45

The fourths compiled above clearly show the improved one Pigment retention caused by the use of the new products according to the invention, made with thin boiling starch bases. The values also show the ability of the products according to the invention continually holding back larger amounts of pigment despite a substantial increase in the amount of alum used.

Example 10

This example describes the suitability of a starch derivative as a paper additive, in which the starch base is converted at the same time through a homolytic oxidation and with aminoalkyl groups has been etherified before esterification.

To produce a starch derivative in the manner described above, 100 parts of corn starch were suspended tap water of about 40 ⁰ C in about 125 parts. The pH of the resulting slurry was adjusted to 11.2 with dilute sodium hydroxide solution. 3 parts of diethylaminoethyl chloride HCl, 0.5 part of calcium hydroxide and 0.5 part of 30% aqueous hydroperoxide were then added to the slurry. While maintaining the pH at the above value, the mixture was stirred for about 17 hours. Then the pH of the reaction mixture was adjusted to 3.0 with dilute hydrochloric acid, and the reaction product was filtered off and thoroughly

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washed. It was determined that the converted starch had a WF value of about 7. This intermediate base was then dissolved in water at a ratio of 1.0 part per Suspended 1.3 parts of water, reacted with 2.0 parts of maleic anhydride and then with 4.0 parts of sodium metabisulfite let react. The diethylaminoethyl sulfosuccinate starch derivative prepared in this way was obtained according to Part 1 of Example 1. This starch derivative had S.G. values for the diethylaminoethy groups and Sulfosuccinate groups of 0.03 and 0.02, respectively. Then was this derivative, a commercially available control sample and a blank sample for the pigment retention properties according to Part 2 of Example 1 examined. The control sample passed from a conventional papermaking composition, which contains an aminoalkyl-etherified and phosphorylated starch additive contained. The blind sample consisted only of the papermaking mass. The following results were obtained obtain:

TiOp retention in the presence

Tested ^{the fol} S ^end Alaunmengen, 4.0% Material 11.0

Test sample control sample blank

The fourth above clearly show the improved pigment retention, the ongoing by using the new products of the invention at both high and low Amounts of alum can be obtained.

74 70 71 61 43 45

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Example 11

This example also describes the suitability of the starch derivative as a paper additive, the starch base being converted at the same time by oxidation and with aminoalkyl groups has been etherified before esterification.

The procedures of Example 10 were repeated with the exception that only 0.1 part of 30% aqueous Hydroperoxides were used without any calcium hydroxide and that etherification only took place over a period of time of 5.75 hours. When tested by the method in Part 2 of Example 1, these showed diethylaminoethyl (S.G.- ¥ ert of about 0.03) -SuIfοsuccinat- (S.G. value of about 0.02) starch derivatives pigment retention values comparable to those of the test sample of Example 10 was.

Example 12

This example describes the improved tear resistance, which is achieved when using the new additives compared to the strength of either untreated sheets or sheets made with a conventional Diethylaminoethyl ether of a phosphorylated starch was obtained.

A lot of a diethylaminoethyl ether and sulfosuccinate derivative with a formulation similar to the test sample of Example 6, following the general procedure produced according to part 1 of example 1.

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With stirring, two sample papermaking compositions H and I were prepared by adding a varied amount of the starch additives described above to an unbleached pulp containing 11.0 parts of alum based on the weight of the dry pulp. The starch additive was added to dilute the pulp at concentrations of 0.5 and 1.5 %, based on the dry weight of the pulp. Sheets were then made from the individual pulp masses on a Williams standard sheet mold.

The strength of these sheets was determined with the Mullen test device according to the procedure according to TAPPI standards T403, ts-63. In the apparatus used, a sheet of paper is clamped between two annular plates, leaving an exposed circular paper surface under which an inflatable rubber diaphragm is located. When air is pumped into this diaphragm, it expands and comes into contact with the exposed surface of the paper. The pressure at which the diaphragm causes the paper to burst or tear is noted. The Mullen factor is then calculated from this by dividing this value by the basis weight of the paper. A higher Mullen factor therefore indicates a stronger paper.

Comparative sheets were prepared according to the same papermaking procedures as described above, in one case a control sample consisting of a standard pulp stock with a conventional diethylaminoethyl ether of the starch additive and in the other case the comparative sample being a standard pulp stock without an additive. The test results, expressed as Mullen values, are as follows:

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• - 29 Mullen
■ Value 2547700 Tested
material Additives
Ji 77.6
92.3 Mullen
factor Test sample H
Test sample I. 0.5
1.5 66.8
76.8 1.44
1.59 Control sample
Control sample 0.5
1.5 1.32
1.45

Blank 60.7 '1.12

The values given above clearly show the improved tear resistance of the sheets that come with the pulp which contained the additive according to the invention.

Although in some cases the new starch derivatives that contain both the cationic or cationogenic aminoalkyl ether groups and which contain sulfosuccinate groups, at low Alum concentrations are not significantly better than starch derivatives, the aminoalkyl ether groups only in combination with phosphate groups, the important fact is to be seen in the fact that the new derivative is used as a pigment retention and strength additives in the presence of both higher and lower concentrations of Alum is effective. These improvements in paper quality, particularly in terms of pigment retention, are greater than before by adding appropriate amounts of other starch derivatives or any combinations of such derivatives to paper pulps could be obtained.

The invention thus provides the practitioner with new paper additives who are able to operate in a wide variety of conditions and are capable of To give paper products, which are characterized by their excellent pigment retention and by increased strength are.

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Claims (10)

Claims 1. <Paper containing alum which contains a starch derivative of a starch base dispersed therein, characterized in that that the starch base has a water flowability between 4 and 40 and that the starch derivative is chemical introduced sulfosuccinate groups and cationogenic or cationic nitrogen-containing substituent groups from the group quaternary ammonium ether groups and amino alkyl ether groups, namely, primary amine, secondary amine and tertiary amine groups. 2.: Paper according to claim 1, characterized in that the degree of substitution of the cationogenic or cationic nitrogen-containing substituent groups in the starch derivative about 0.005 to 1.50 and that the degree of substitution of the sulfosuccinate groups is at least 0.008. 3. Paper according to claim 1 or 2, characterized in that the aminoalkyl ether groups are diethylaminoethyl groups are. 4. Paper according to claim 31, characterized in that the degree of substitution of the diethylaminoethyl groups in the starch derivative is about 0.005 to about 1.50. 5. Process for the manufacture of paper, in which one of the mass at any stage before the formation of a Tissue added a starch derivative of a starch base, characterized in that a starch base with a Water flowability between 4 and 40 used and that 60981 8/1028 the starch derivative chemically introduced sulfosuccinate groups • and cationogenic or cationic nitrogen-containing substituent groups from the group of quaternary ammonium ether groups and aminoalkyl ether groups, namely primary amine, secondary> amine and tertiary amine groups. 6. The method according to claim 5 »characterized in that the degree of substitution of the cationogenic or cationic nitrogen-containing substituent groups in the starch derivative about 0.005 to 1.50 and that the degree of substitution of the Sulfosuccinate groups is at least 0.008. 7. The method according to claim 5, characterized in that the aminoalkyl ether groups are diethylaminoethyl groups. 8.y starch derivative of a starch base, characterized in that that the starch base has a water flowability between 4 and 40 and that the starch derivative is chemically introduced Sulfosuccinate groups and cationogenic or cationic nitrogen-containing substituent groups from the Group of quaternary ammonium ether groups and aminoalkyl ether groups, namely primary amine, secondary amine and tertiary Amine groups. 9. starch derivative according to claim 8, characterized in that that the degree of substitution of the cationogenic or cationic nitrogen-containing substituent groups in the starch derivative about 0.005 to 1.50 and that the degree of substitution of the sulfosuccinate groups is at least 0.008 amounts to. 10. Starch derivative according to claim 8, characterized in that the aminoalkyl ether groups are diethylaminoethyl groups are. 609818/1028