DE102009000978A1 - Aqueous compositions containing amino functional organopolysiloxanes and starch - Google Patents

Abstract

Described are aqueous compositions comprising (A) water-insoluble, linear or branched organopolysiloxane having an amine number of at least 0.1 mequiv./g, having at least one SiC-bonded hydrocarbon radical with basic nitrogen and at least one silyl end group with an alkoxy or hydroxy radical, (B) protonating agent, (C) starch and (D) water with the proviso that further emulsifiers and / or solvents in amounts of at most 1 part by weight per 100 parts by weight of organopolysiloxane (A), preferably no further emulsifiers and solvents are used.

Description

The The invention relates to aqueous compositions containing amino-functional organopolysiloxanes and their use as sizing agents for paper.

silicones As is known, they are outstandingly suitable as water repellents. Your use z. B. as building protection or textile equipment has been state of the art for decades.

Your Use in paper sizing agents is also known. you will be preferably used in water-based formulations. Especially are also emulsions of amino-functional polydimethylsiloxanes for this application has been described.

EP 1 081 283 A1 (Dow Corning Toray Silicone) describes formulations consisting of water-soluble, linear, alkyl or aralkyl group-containing, amino-functional polysiloxanes, a sizing agent and water. However, water-soluble polydimethylsiloxanes are limited in their hydrophobing effect due to their hydrophilic properties.

EP 1 088 939 A1 (Dow Corning Toray Silicone) describes formulations consisting of water-insoluble, linear, alkyl- or aralkyl-containing, amino-functional polysiloxanes, a sizing agent with emulsifying properties, and preferably a surfactant and water for printing papers. The polysiloxanes used must contain, in addition to the methyl group, alkyl or aralkyl groups having two or more carbon atoms and carry at the ends of dimethylalkyl or dimethylaralkyl groups. The preparation of dimethylalkyl- or dimethylaralkyl-terminated aminofunctional polysiloxanes is state of the art, but the introduction of alkyl or aralkyl groups in place of methyl groups into the polysiloxanes requires an additional process step compared with the preparation of amino-functional polysiloxanes containing pure dimethyl groups. The surfactants used generally have a disturbing effect on paper sizing, since they reduce the hydrophobizing effect of the polydimethylsiloxane due to their hydrophilic groups in the molecule.

In the US 7,319,119 B (Wacker Chemie AG) contain volatile aids that evaporate when coating the paper on the paper machine, get back to the paper in concentrated form during the production process and thus can cause uncontrollable negative effects on the finished paper.

EP 0 099 049 A1 (Dow Corning Corporation) describes the preparation of silicones-treated starches and their use as sizing agents. In order to produce durable emulsions, emulsifiers or solvents are generally required in addition. An additional process step is therefore necessary for the production of these products, and the substances used for this purpose, such as surfactants which reduce the hydrophobizing properties of the silicone component, or solvents which may impair the quality of the finished paper, have adverse effects.

It The task therefore consisted of aqueous compositions amino-functional organopolysiloxanes and suitable emulsifiers to provide that do not have the disadvantages described above. Farther The object was to provide compositions which are preferably for the hydrophobic treatment of celluloses, in particular as Sizing agent for paper can be used.

• (A) wasserunlösliches, lineares oder verzweigtes Organopolysiloxan mit einer Aminzahl von mindestens 0,1 mequiv./g, das mindestens einen SiC-gebundenen Kohlenwasserstoffrest mit basischem Stickstoff und mindestens eine Silylendgruppe mit einem Alkoxy- oder Hydroxyrest aufweist,
• (B) Protonierungsmittel,
• (C) Stärke und
• (D) Wasser

mit der Maßgabe, dass weitere Emulgatoren und/oder Lösungsmittel in Mengen von jeweils höchstens 1 Gewichtsteil je 100 Gewichtsteile Organopolysiloxan (A), vorzugsweise keine weiteren Emulgatoren und Lösungsmittel, eingesetzt werden.An object of the invention are aqueous compositions containing

• (A) water-insoluble, linear or branched organopolysiloxane having an amine number of at least 0.1 mequiv./g, which has at least one SiC-bonded hydrocarbon radical with basic nitrogen and at least one silyl end group with an alkoxy or hydroxy radical,
• (B) protonating agent,
• (C) strength and
• (D) water

with the proviso that further emulsifiers and / or solvents in amounts of at most 1 part by weight per 100 parts by weight of organopolysiloxane (A), preferably no further emulsifiers and solvents are used.

The compositions according to the invention are based on water-insoluble, easily preparable, amino-functional polydimethylsiloxanes having a strong hydrophobic effect and are emulsified in starch Otherwise, they do not contain any of the additives described in the prior art, such as surfactants, solvents or other volatile auxiliaries which may reduce the hydrophobizing effect of the compositions according to the invention or otherwise impair the papermaking process.

The Starch is used as emulsifier or protective colloid.

As organopolysiloxane (A) is preferably those of units of the formula R ¹ _a R ² _b SiO _{(4-ab) / 2} , (I) where R ^{1 is} identical or different and denotes an alkyl radical having 1 to 40 carbon atoms or a radical -OR ',
R 'is a hydrogen atom or an alkyl radical having 1 to 18 carbon atoms,
R ^{2 is the} same or different and is a linear, cyclic or branched, unsubstituted or substituted aminoalkyl, preferably an aminoalkyl of the general formula -R ³ -NR ⁴ R ⁵ (III), where R ³ denotes a divalent linear, cyclic or branched, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 40 carbon atoms,
R ^{4 represents} a hydrogen atom or a monovalent linear, cyclic or branched, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 40 carbon atoms,
R ^{5 is} the radical R ⁴ or a radical of the general formula - (R ⁶ -NR ⁴ ) _x R ⁴ (III), where R ^{6 has} the meaning of R ³ , preferably a bivalent hydrocarbon radical having 1 to 6 carbon atoms,
x is 0 or an integer from 1 to 40,
a is 0, 1, 2 or 3,
b is 0, 1, 2 or 3,
with the proviso that the sum of a + b has an average value of 1.5 to 2.5, and that the ratio of a to b is such that the organopolysiloxane has at least an amine number of 0.1 meq./g of organopolysiloxane having
and that in at least one terminal unit R ^{1 is} a radical of the formula -OR ',
is used.

R ' is preferably a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms.

Examples for alkyl radicals R 'are the methyl or ethyl radical.

The alkyl radical R ¹ is preferably a linear, branched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, particularly preferably a methyl radical.

R ¹ can also be an alkoxy radical, preferably a methoxy or ethoxy radical, or a hydroxyl radical.

Preferably, R ^{1 is} a methyl radical or an alkoxy radical, preferably a methoxy or ethoxy radical, or a hydroxyl radical.

Prefers contains at least one terminal unit in the Organopolysiloxane (A) an alkoxy radical, preferably a methoxy or ethoxy radical, or a hydroxyl radical.

The divalent hydrocarbon radical R ³ may be linear, cyclic, branched, aromatic, saturated or unsaturated. The radicals R ³ preferably have 1 to 6 carbon atoms. The radical R ^{3 is} preferably an alkylene radical, particularly preferably a propylene radical.

The monovalent hydrocarbon radical R ⁴ may be linear, cyclic, branched, aromatic, saturated or unsaturated. Preferably, the hydrocarbon radicals R ^{4 have} 1 to 6 carbon atoms, with alkyl radical being preferred. Preferred examples of radicals R ⁴ are hydrogen, methyl or ethyl radicals.

Preferably, the divalent hydrocarbon radical R ⁶ is an alkylene group having 1 to 6 carbon atoms, such as methylene or ethylene radical.

Preferably x is 0 or an integer from 1 to 18, preferably 0, 1, 2, 3, 4, 5 or 6.

Preferred radicals R ² are
-CH ₂ NR ⁴ ₂ , - (CH ₂ ) ₃ NR ⁴ ₂ , - (CH ₂ ) ₃ NR ⁴ (CH ₂ ) ₂ NR ⁴ ₂ ,
wherein R ^{4 has} the meaning given above.

Examples of radicals R ² are
H ₂ N (CH ₂ ) ₃ -
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) CH (CH ₃ ) CH ₂ -
(Cyclohexyl) NH (CH ₂ ) ₃ -
CH ₃ NH (CH ₂ ) ₃ -
(CH ₃ ) ₂ N (CH ₂ ) ₃ -
CH ₃ CH ₂ NH (CH ₂ ) ₃ -
(CH ₃ CH _{2) 2} N (CH _{2) 3} -
CH ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ -
(CH ₃ ) ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -
CH ₃ CH ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ -
(CH ₃ CH ₂ ) ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -

Prefers is the organopolysiloxane (A) from at least 3, in particular from at least 10 units of the formula (I) built.

Preferred organopolysiloxanes (A) are linear organopolysiloxanes of the general formula ZR ₂ SiO (R ₂ SiO) _k (RR ² SiO) ₁ SiR ₂ Z (IV), used, where
R is an alkyl radical having 1 to 18 carbon atoms, preferably a methyl radical,
R ^{2 has} the meaning given above,
Z is a radical -OR ', where R' is a hydrogen atom or an alkyl radical having 1 to 18 carbon atoms, preferably a hydrogen atom or a methyl or ethyl radical,
k and l are integers,
with the proviso that k and I assume such values that the organopolysiloxane has at least an amine number of 0.1 mequiv./g organopolysiloxane.

Prefers the sum (k + l) is an integer from 2 to 2000, in particular from 2 to 200.

In the context of this invention, formula (IV) should be understood such that k units - (R ₂ SiO) - and l units - (RR ² SiO) - can be distributed in any desired manner, for example as a block or randomly, in the organopolysiloxane molecule.

Within or along the siloxane chain of the siloxanes of the formula given above, which is usually not represented by such formulas, other siloxane units may be present in addition to the diorganosiloxane units R ₂ SiO. Examples of such other, mostly only as impurity present siloxane units are those of the formulas RSiO _3/2 , R3SiO _1/2 and SiO ₂ , wherein R has the meaning given above.

Preferably the organopolysiloxanes (A) have an amine number of at least 0.3 mequiv / g organopolysiloxane, wherein the amine number is at most 7 mequiv / g organopolysiloxane.

The Viscosity of the organopolysiloxane is preferably 1 to 100,000 mPa · s at 25 ° C, preferably 10 to 10 000 mPa · s at 25 ° C.

It may be contained in the compositions of the invention further organopolysiloxanes. These may contain SiC-bonded glucoside groups or, in addition to the amino groups in the molecule, SiC-bonded polyether groups, preferably polyoxyethylene and / or polyoxypropylene groups contain.

The protonating agent (B) is a monoprotic or polyprotic, water-soluble or water-insoluble, organic or inorganic acid,
preferably a monoprotic, water-soluble, organic acid, more preferably acetic acid.

Protonating agent is preferably added in an amount of 0.05 to 2 moles of proton per mole of basic nitrogen atom of R ² .

The starches used as emulsifiers and protective colloids (C) can come from a variety of plants. Examples are corn, potato, wheat, rice or tapioca starches.

It may be native, partially degraded or chemically altered Act strength. Particularly preferred are partially degraded, chemically modified corn or potato starches, in particular anionic, partially degraded, chemically modified potato starches. Preference is given to non-retrograding, amylopectin-rich starches.

Strength is preferred in amounts of preferably 1 to 50 parts by weight from 3 to 10 parts by weight, per 100 parts by weight organopolysiloxane (A) used.

The Water (D) is deionized or saline water, preferably completely desalinated water.

water is preferred in amounts of preferably 30 to 99 parts by weight from 50 to 90 parts by weight, per 100 parts by weight organopolysiloxane (A) used.

The Composition according to the invention may be one of Silanol and Si alkoxy groups substantially free MQ silicone resin (E) included.

The MQ silicone resin (E) contains units of the formulas
M = R ₃ SiO _1/2 , wherein R has the meaning given above, and
Q = SiO _4/2 ,
wherein the ratio of the units M to Q is between 0.5 and 1.5 and the MQ silicone resin still insignificant proportions of alkoxy radicals -OR 'and hydroxy radicals -OH and
insignificant proportions of units of the formulas
D = R ₂ SiO _2/2 and
T = RSiO may have _3/2 .

Preferably At most 2.5% by weight of the radicals R in the MQ resin are alkoxy radicals -OR 'or hydroxy radicals -OH.

Preferably are at most 5% by weight of the units in the MQ resin D or T units.

If MQ resins are used, they are in amounts of preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, used per 100 parts by weight of organopolysiloxane (A).

Further can the compositions of the invention Biocides and other additives commonly used in papermaking such as fillers, optical brighteners, wet strength and the like contain.

The compositions according to the invention can be prepared by conventional emulsification processes at temperatures below 60 ° C. Heating to temperatures above 60 ° C, as in EPO 0 099 049 is not necessary. Preference is given to temperatures at which no retrogradation of the types of starch used occurs.

The Compositions according to the invention have the Advantage that they are storage-stable and dilution-stable oil-water mixtures, preferably oil-in-water emulsions.

The Compositions according to the invention are suitable for the hydrophobic treatment of porous and not porous, absorbent and non-absorbent Substrates, preferably celluloses, in particular paper.

One Another object of the invention is therefore a process for hydrophobicizing Treatment of celluloses and paper with the invention Compositions.

Prefers is the use of the compositions of the invention as a sizing agent for paper.

One Another object of the invention is therefore the sizing of paper, by containing the surface of paper with sizing agents the compositions of the invention in contact is brought and then dried.

The Drying takes place at temperatures of preferably 20 to 200 ° C, preferably 75 to 110 ° C.

The Compositions according to the invention can diluted according to the degree of sizing to be achieved and optionally after the addition of further starches or others in papermaking conventional additives by the in papermaking processes known as a surface sizing agent or engine sizing agent. The use is preferred as a surface sizing agent. The order is preferred by means of a doctor blade, in particular the order by means of a size press.

When Papers can contain all types of cellulosic papers such as office papers, printing papers, veneer base papers, packaging papers or cardboard boxes are used. They are particularly suitable for Veneer base papers, packaging papers and cardboard, in particular for cardboard boxes.

Examples

Description of the starting materials:

Aminofunctional organopolysiloxane (A1):

The employed linear aminofunctional dimethylpolysiloxane has a viscosity of about 1000 mm ² / s at 25 ° C, with pendant functional radicals - (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ and an amine number of 0.3 mequiv./g Organopolysiloxane on. In addition, the organopolysiloxane contains as end groups reactive OMe / OH radicals.

SiC-bonded polyether groups containing Polysiloxane (A2):

The dimethylpolysiloxane used has a chain length of about 75 Si-O units, contains as side-functional radicals about two functional groups - (CH ₂ ) ₃ O-CH ₂ -CH (OH) -CH ₂ -N- (CH ₂ -CH ₂ -OH) ₂ and about 2 functional groups - (CH ₂ ) ₃ O- (CH ₂ -CH ₂ -O) ₂ O- (CH ₂ -CH (CH ₃ ) -CH ₂ O) ₂₀ -H ,

In addition, the organopolysiloxane contains -Si (CH ₃ ) ₃ radicals as end groups.

Glucoside-functional organopolysiloxane (A3):

The dimethylpolysiloxane used has a chain length of about 55 Si-O units and contains as lateral, functional radicals about 25 functional groups - (CH ₂ ) ₃ O-CH ₂ -CH ₂ -O-glucoside. In addition, the organopolysiloxane contains -Si (CH ₃ ) ₃ radicals as end groups. It is used in a 50% aqueous solution.

Used in the comparative experiment, according to Protonation of water-soluble, amino-functional organopolysiloxane (A4):

The amino-functional dimethylpolysiloxane used is an equilibrium of -OH endblocked dimethylpolysiloxane having a viscosity of about 80 mm ² / s at 25 ° C. and 3- (2-aminoethyl) aminopropyltrimethoxysilane in a ratio of about 2: 1, which has a viscosity of about 30 mm ² / s at 25 ° C and an amine value of about 3 mequiv./g organopolysiloxane has. It contains as end groups reactive OMe / OH residues.

Starch used for emulsification:

The starch is Perfectafilm X 115, AVEBE, an anionic potato starch derivative.

Examples B1 to B4 and comparative experiment V1:

Preparation of the various compositions:

Step 1:

First, the starch solution is prepared as follows:
The cold water is placed in a heatable vessel, then the starch powder Perfectafilm X 115 added and stirred well by means of paddle stirrer.

The Starch powder does not dissolve in cold water, but is dispersed by good stirring.

If the starch is well distributed slowly until about 80-85 ° C heated.

at At this temperature, the starch is opened up and it A thick, clear starch solution is produced.

Step 2:

at a temperature between 50-60 ° C becomes this Starch solution first the aminosiloxane A1 or A4 added and emulsified by means of Ultra-Turrax. Subsequently If necessary, the additional siloxane component A2 or A3 is added and also emulsified by means of Ultra-Turax.

To the acetic acid is added and the Emulsion well homogenized again.

Then is diluted slowly and in portions with water and Finally, the preservatives are added.

Variants with MQ resin:

In a third step, the MQ resin (of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units in a ratio of 0.5: 1.0) is prepared in the form of a 55% solution in Exxol 100 DS (hydrocarbon) was added to the finished emulsion and incorporated by means of paddle stirrer.

According to the invention, aqueous Composition B1:

• 15.00% of amino-functional organopolysiloxane A1
• 35.00% Perfectafilm X 115 (20% solution, according to 7% strength)
• 0.13% acetic acid conc.
• 0.08% biocide Kathon LXE (Rohm and Haas)
• 0.05% preservative (methylisothiazolone) with 10
• 49.74% deionized water

According to the invention, aqueous Composition B2:

• 15.00% of amino-functional organopolysiloxane A1
• 0.90% MQ resin solution
• 35.00% Perfectafilm X 115 (20% solution, according to 7% strength)
• 0.13% acetic acid conc.
• 0.08% biocide Kathon LXE (Rohm and Haas)
• 0.05% preservative with 10 (10% solution of 2-methyl-4) isothiazolin-3-one in water, Rohm and Haas)
• 48.84% deionized water

According to the invention, aqueous Composition B3:

• 15.00% of amino-functional organopolysiloxane A1
• 5.00% SiC-bonded polyether-containing polysiloxane (A2)
• 30.00% Perfectafilm X 115 (20% solution, corresponding to 7% strength)
• 0.13% acetic acid conc.
• 0.08% biocide Kathon LXE (Rohm and Haas)
• 0.05% preservative with 10 (10% solution of 2-methyl-4) isothiazolin-3-one in water, Rohm and Haas)
• 49.74% deionized water

According to the invention, aqueous Composition B4:

• 20.00% of amino-functional organopolysiloxane A1
• 3.00% Glucoside-functional organopolysiloxane (A3), aqueous solution
• 27.00% Perfectafilm X 115 (20% solution, corresponding to 7% strength)
• 0.18% acetic acid conc.
• 0.08% biocide Kathon LXE (Rohm and Haas)
• 0.05% preservative with 10 (10% solution of 2-methyl-4) isothiazolin-3-one in water, Rohm and Haas)
• 49.69% deionized water

Comparative experiment V1 with one after protonation water-soluble, amino-functional organopolysiloxane:

• 20.00% after protonation of water-soluble amino-functional Organopolysiloxane (A4)
• 30.00% Perfectafilm X 115 (20% solution, corresponding to 7% strength)
• 1.80% acetic acid conc.
• 0.08% biocide Kathon LXE (Rohm and Haas)
• 0.05% preservative with 10 (10% solution of 2-methyl-4) isothiazolin-3-one in water, Rohm and Haas)
• 48.31% deionized water

Surface sizing - test procedure:

All Sizing attempts were usually made within one day Preparation of the emulsions carried out.

Making the sizing fleets:

a) Sizing without starch:

The emulsions to be tested are diluted in demineralized water and applied to the paper.
Depending on the active ingredient content of the emulsions, dilution liquors are prepared for this purpose so that the active substance coating on paper is about 0.2% of the 100% strength amine oil.

b) sizing with starch:

used was an oxidized potato starch, Perfectamyl A 4692, Fa. AVEBE.

to Starch sizing is dispersed in cold water and then open with slow heating. It becomes a solution used by 6-8%.

After that become the emulsions to be tested in the sizing liquor diluted with the starch solution so that the active ingredient coating on paper about 0.2% of 100% amine oil is.

Gluing the papers:

An unsized veneer base paper (basis weight 50 g / m ² ), a testliner (basis weight 164 g / m ² ) and a winding cardboard (basis weight 178 g / m ² ) were used. The sizing is carried out by means of a size press (also called padder), which consists of two counter-rotating rollers with an adjustable nip. The paper is guided through the nip in which the sizing liquor is at a set speed of 3 m / min and a contact pressure of the rollers of 2 bar. The temperature of the liquor is at room temperature or 55 ° C in starchy liquors. By weighing the paper before and after the padding, the liquor pickup is determined in%.

Drying the papers:

To For padding, the papers are dried in a belt dryer.

Dried It is heated for 45 s at a temperature of approx. 90 ° C.

Testing the sizing effect:

Cobb test: Water absorption after DIN 20535 (Cobb-Unger method):
The paper is stored overnight in standard climate (23 ° C and about 50% relative humidity) and tested the next day.

Out the treated pieces of paper are covered with a template Teared test pieces and on an analytical balance weighed.

Subsequently the paper sample is placed in the Cobb Tester. This one exists from a metal jar containing 240 ml of water.

Then the paper sample is placed and the device is closed and swiveled so that the paper is supplied with the water. A Cobb ₆₀ is measured, ie the exposure time of the water to the paper surface is 60 sec.

To Time lapse, the device is swung back, taken the paper sample and then between 2 filter paper layers placed and with a 10 kg roll abgegautscht (squeezed). After that the paper is weighed again.

The weight gain corresponds to the Cobb value in g / m ² .

The results are summarized in Tables 1 to 3. Table 1: Sizing of veneer base paper: (untreated Cobb60: 63 g / m ² ) composition Cobb ₆₀ in g / m ² without starch with strength B1 43 41 B2 49 45 B3 34 43 B4 38 32 Comparative Experiment V1 57 58 Table 1: Sizing of testliner: (untreated Cobb ₆₀ : 190 g / m ² ) composition Cobb ₆₀ in g / m ² without starch with strength B1 25 23 B2 - 23 B3 29 22 B4 22 24 Comparative Experiment V1 23 28 Table 1: Gluing of winding cardboard: (untreated Cobb: 220 g / m ² ) composition Cobb ₆₀ in g / m ² without starch with strength B1 33 23 B2 - 29 B3 - 32 B4 24 23 Comparative Experiment V1 36 39

The results show that with the compositions according to the invention the Cobb ₆₀ value is the lowest, ie the hydrophobizing effect and thus the sizing action is the greatest.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 1081283 A1 [0004]
• EP 1088939 A1 [0005]
• US7319119 B [0006]
• EP 0099049 A1 [0007]
• EP 0099049A [0046]

Cited non-patent literature

• - DIN 20535 [0077]

Claims (9)

Aqueous compositions containing (A) water-insoluble, linear or branched organopolysiloxane with an amine value of at least 0.1 mequiv./g, which is at least a SiC-bonded hydrocarbon radical with basic nitrogen and at least one silyl end group having an alkoxy or hydroxy group having, (B) protonating agent, (C) strength and (D) water with the proviso that more Emulsifiers and / or solvents in amounts of each at most 1 part by weight per 100 parts by weight organopolysiloxane (A), preferably no further emulsifiers and solvents, be used. Aqueous compositions according to claim 1, characterized in that as organopolysiloxane (A) such from units of the formula R ¹ _a R ² _b SiO _{(4-ab) / 2} , (I) and wherein R ^{1 is the} same or different and is an alkyl radical having 1 to 40 carbon atoms or a radical -OR ', R' is a hydrogen atom or an alkyl radical having 1 to 18 carbon atoms, R ^{2 is the} same or different and is a linear, cyclic or branched, unsubstituted or substituted aminoalkyl radicals, preferably an aminoalkyl radical of the general formula -R ³ -NR ⁴ R ⁵ (III), wherein R ^{3 is} a divalent linear, cyclic or branched, unsubstituted or substituted, saturated or unsaturated hydrocarbon radical having 1 to 40 carbon atoms, R ^{4 is} a hydrogen atom or a monovalent linear, cyclic or branched, unsubstituted or substituted, saturated or unsaturated hydrocarbon radicals 1 to 40 carbon atoms, R ^{5 is} the radical R ⁴ or a radical of the general formula - (R ⁶ -NR ⁴ ) _x R ⁴ (III), where R ^{6 has} the meaning of R ³ , preferably a divalent hydrocarbon radical having 1 to 6 carbon atoms, x is 0 or an integer from 1 to 40, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, with the proviso that the sum a + b has an average value of 1.5 to 2.5, and that the ratio of a to b is chosen such that the organopolysiloxane has at least an amine value of 0.1 mequiv./g organopolysiloxane and that in at least one terminal unit R ^{1 is} a radical of the formula -OR ', is used. Aqueous compositions according to claim 1 or 2, characterized in that as organopolysiloxane (A) a linear organopolysiloxane of the general formula ZR ₂ SiO (R ₂ SiO) _k (RR ² SiO) ₁ SiR ₂ Z (IV), wherein R is an alkyl radical having 1 to 18 carbon atoms, preferably a methyl radical, R ^{2 has} the meaning given in claim 2, Z is a radical -OR ', wherein R' is a hydrogen atom or an alkyl radical having 1 to 18 Carbon atoms, preferably a hydrogen atom or a methyl or ethyl radical, k and l are integers, with the proviso that k and l assume such values that the organopolysiloxane has at least an amine number of 0.1 mequiv./g organopolysiloxane. Aqueous compositions according to claim 1, 2 or 3, characterized in that as native strength, partially degraded or chemically modified maize or Potato starch is used. Aqueous compositions according to one of Claims 1 to 4, characterized in that MQ resins be used. Aqueous compositions according to any one of claims 1 to 5, characterized in that as further organopolysiloxanes organopolysiloxanes having SiC-bonded glucoside or SiC-bonded polyether groups or organopolysiloxanes which in addition to the amino groups R ² (wherein R ^{2 has} the meaning given in claim 2) SiC-bonded polyether groups have used. Process for the hydrophobic treatment of celluloses and paper having compositions according to any one of claims 1 to 6. Method for sizing paper, characterized that the surface of paper with a sizing agent containing compositions according to any one of claims 1 until 6 is brought into contact and then the paper is dried. Process for hydrophobing the treatment of porous and non-porous, absorbent and non-absorbent substrates with compositions according to any one of claims 1 to 6.