WO1997046757A1

WO1997046757A1 - Composition, use of a cellulose ether as thickening agent and production of a coated cellulose-based two-dimensional product

Info

Publication number: WO1997046757A1
Application number: PCT/SE1997/000847
Authority: WO
Inventors: Kerstin Larsson; Erland Hermansson; Dan Eklund; Peter Dahlvik
Original assignee: Akzo Nobel Surface Chemistry Ab
Priority date: 1996-06-05
Filing date: 1997-05-23
Publication date: 1997-12-11
Also published as: DE69725748T2; CA2253814C; SE9602221L; BR9709526A; NO325271B1; SE506674C2; EP0929716A1; CA2253814A1; EP0929716B1; NO985138L; SE9602221D0; NO985138D0; DE69725748D1; JP2000511601A; US6123996A; AU3197797A

Abstract

The present invention relates to an aqueous composition for coating, such as sizing or application of a layer of a coating slip, of cellulose-based two-dimensional products. The composition has improved properties at increased temperatures and at high shear rates. These properties are achieved by using as tickening agent a cellulose ether which is substituted with hydroxyalkyl groups, such as hydroxyethyl and hydroxypropyl, and alkyl groups having 1-3 carbon atoms, and which has a cloud point in the range from 35 °C to 80 °C.

Description

COMPOSITION, USE OF A CELLULOSE ETHER AS THICKENING AGENT AND PRODUCTION OF A COATED CELLULOSE-BASED TWO-DIMENSIONAL PRODUCT

The present invention relates to an aqueous composi¬ tion for coating, such as surface sizing or application of a layer of a coating slip, of cellulose-based two-dimensional products. The composition has improved properties at in¬ creased temperatures and at high shear rates. These proper- ties are achieved by using as thickening agent a cellulose ether, which is substituted with hydroxyalkyl groups, such as hydroxyethyl and hydroxypropyl, and alkyl groups having 1-3 carbon atoms.

In coating, such as application of a layer of a coat- ing slip or surface sizing of cellulose-based two-dimension¬ al products, such as paper or cardboard, with a composition, the primary object is to change the properties of the paper product, such as improved strength, improved appearance, improved printability, improved impermeability or improved adhesion properties. Thus, it is common to surface-size paper or cardboard with an aqueous binder-containing compo¬ sition for improving, inter alia, the wet strength, or to coat paper or cardboard with a composition, which contains pigment pastes, for improving the printability and the appearance of the surface. The coating slip compositions can, in addition to binder and pigments, also contain secondary binders (co-binders) , protective colloids, thickening agents and dispersing agents. As thickening agent, protective colloid or secondary binder it is common to add water-soluble or water-swellable polymers based on polyvinyl alcohol, modified celluloses, starch, casein, alginate or high-molecular carboxyl-group-containing poly- merisates.

The use of cellulose ethers in coating slips is dis- closed in e.g. EP 15 517, where carboxymethylcellulose is added as a secondary binder. From EP 307 795 it is known to use as protective colloid, inter alia, methyl cellulose. EP 425 997 discloses that hydrophobically modified alkyl- cellulose, alkylhydroxyalkylcellulose or hydroxyalkylcellu- lose can be used as thickening agent in aqueous paper coat¬ ing compositions. The hydrophobing groups are preferably C₁₂_ ₁₆-alkyl groups or alkylaryl groups. When used in coating slip compositions, these cellulose ethers result in an im¬ proved viscosity at high shear rates, compared with carboxy- ethylcellulose ethers. Even if paper coating slip composi¬ tions according to EP 425 997 result in paper coating slip compositions having properties that in some respects are better than those of carboxymethylcellulose, they also have certain limitations. Thus, they give a comparatively low viscosity at the increased temperatures prevailing when dry¬ ing the compositions. From EP 496 269 it is also known to produce, for the coating of paper, a multipolysaccharide-containing suspen¬ sion, which contains a low molecular polysaccharide, which is dissolved in the aqueous phase and which can be a car¬ boxymethylcellulose or a hydroxyethylcellulose. Moreover, the coating composition contains one or more dispersed, i.e. not dissolved, cellulose polymers, such as hydroxypropyl- cellulose, methylcellulose, methylhydroxypropylcellulose and hydrophobically modified hydroxyethylcellulose.

According to the present invention, it has now been found that compositions for coating, such as application of a layer of a coating slip or surface sizing, of cellulose- based products, such as paper and board, with improved properties in respect of viscosities at increased tempera¬ tures and at high shear rates can be obtained if use is made as thickening agent of a water-soluble, nonionic alkyl¬ hydroxyalkylcellulose, which contains alkyl groups having 1- 3 carbon atoms and hydroxyalkyl groups containing 2-3 carbon atoms, but which is free from hydrophobically modifying hydrocarbon groups having at least 4 carbon atoms, the cellulose ether having a cloud point in the range from 35 to 80°C, preferably from 45 to 70^CC. The alkylhydroxyalkyl¬ cellulose thus is dissolved in the composition and its vis- cosity can vary within wide ranges, such as from 5 mPa*s to 150,000 mPa»s, but usually is 10-10,000 mPa-s in 2% aqueous solution at 20°C.

Compositions that are produced while using the above- described cellulose ethers as thickening agent have a low viscosity at high shear rates and a low tendency to splash, which makes them suitable to apply on two-dimensional cellu¬ lose products, such as paper and board. The viscosity in¬ crease which arises in the composition when the coated cellulose product is heated during the drying stage, stabi¬ lises and immobilises the applied layer and facilitates the subsequent treatment. Despite the increasing viscosity, the inventive compositions have as good dewatering or even more rapid dewatering than compositions containing other types of cellulose ethers and not having the same viscosity increase at an increased temperature.

Typical cellulose ethers for use in compositions ac¬ cording to the invention are ethylhydroxyethylcellulose, ethylethylhydroxyethylcellulose, methylethylhydroxyethyl- hydroxypropylcellulose and methylhydroxypropylcellulose. As a rule, the hydroxyethyl groups constitute at least 30% of the total number of hydroxyalkyl groups, and the number of ethyl substituents usually constitutes at least 10% of the total number of alkyl substituents. Examples of such cellu- lose ethers are ethylhydroxyethylcellulose with DS_ethyl = 0.8- 1.3 and MS_hydroxyethyi = 1.9-2.9 and methylethylhydroxyethyl- cellulose with DS_methyl = 1.0-2.5; DS_ethyl = 0.1-0.6 and MS_{hydrOJtyβthy}ι = 0.1-0.8. The amount of alkylhydroxyalkylcellu- lose usually is from 0.05 to 3, preferably from 0.2 to 1.5% by weight of the composition. The cellulose ethers can be produced in conventional manner by reacting mercerised cellulose with ethylene oxide and/or propylene oxide and methylchloride, ethylchloride and/or propylchloride.

The water-based compositions according to the inven- tion suitably contain a binder in an amount 2-70, preferably 5-30% by weight. The binder may consist both of water- soluble binders and of binders in the form of water dispersions or latex. Examples of suitable binders are copolymerisates of ethylenically unsaturated carboxylic acids, starch, proteins, casein and carboxymethylcellulose. Examples of suitable copolymerisates are those made up of monomers from the group of esters of acrylic acid and metha¬ crylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, C₃-C₅ ethylenically unsaturated monocarboxy- lic acids, ethylenically unsaturated dicarboxylic acids and their semi-esters, vinylchloride, ethylenically unsaturated hydrocarbons, vinyl ester, vinyl sulphonic acid and esters of unsaturated carboxylic acids which are derived from multivalent alcohols. When the compositions are to be used for surface sizing of cellulose-based two-dimensional products, they also contain 5-65% by weight size, based on the dry solids content of the composition. Examples of suitable sizes are different types of colophonium, sulphate resin, protein complex, polyethylene wax dispersions, paraffin copoly ers, melamine-formaldehyde resins etc.

The compositions may also contain pigments, which may consist of naturally derived inorganic pigments as well as synthetically produced pigments. Examples of pigments are kaolin, calcium carbonate, talc, titanium dioxide, satin white, hydratised aluminium, sodium silicoaluminate and plastic pigments and a large number of special pigments, such as barium sulphate and zinc oxide. In a pigment coating slip composition, the content of pigments usually is 5-65% by weight and constitutes 4 to 20 times the amount of binder.

A typical coating slip composition according to the invention is composed as follows, based on its dry solids content.

0.07-5, preferably 0.3-2% by weight alkylhydroxyalkylcellu- lose as defined 5-15, preferably 7-13% by weight latex, 60-94, preferably 70-90% by weight pigment,

0-10, preferably 0-7% by weight secondary binder, 0-3, preferably 0.1-2% by weight dispersing agent, 0-5, preferably 0-2% by weight protective colloid, 0-4, preferably 0-2% by weight other additives, such as fluorescent whitening agents, bactericides, antifoaming agents and lubricants, the dry solids content being from 20 to 70% by weight. The Brookfield viscosity of the coating slip composition normally is from 100 to 2,500 mPa^»s at 100 rpm and 20°C. The viscosity of coating slip compositions having a dry solids content from 55 to 70% by weight is from 600 to 2500 mPa»s. An aqueous coating slip composition according to the inven¬ tion can be produced by dispersing a pigment in water, optionally with the aid of a dispersing agent. The resulting slip can then be supplied with water-soluble binders in¬ cluded in the composition, alkylhydroxyalkylcellulose and other additives and, finally, optional binder dispersions such as latex.

A cellulose-based product coated with a composition according to the invention can be produced by a) applying a composition according to the invention at a temperature below the cloud point of the alkylhydroxyalkylcellulose to the cellulose-based product, b) drying the two-dimensional cellulose product coated with the composition during heating, and c) if desired, calendering said cellulose product.

The application of the composition takes place in a manner known per se, for instance by air knife coating, roll coat¬ ing or blade coating. Usually, at least 90% of the drying takes place at a temperature range which to at least 60%, preferably completely, falls below the cloud temperature of the alkylhydroxyalkylcellulose. Depending on the season and the geographic position, the temperature of the composition in application usually is in the range of 5-30, preferably 10-25°C. The invention is further illustrated by the following examples. Example l

A number of aqueous coating slip compositions with a dry solids content of 60% by weight and intended for coating of paper were produced, based on the following recipe. 100 parts by weight kaolin

10 parts by weight styrene-butadiene latex

0.11 parts by weight sodium acrylate

0.6-1.1 parts by weight cellulose ether (the amount adjusted to give the composi- tion a viscosity according to

Brookfield 100 of about 1100 mPa»s) balance water to a dry solids content of 60% by weight. The following cellulose ethers were used. All visco¬ sities concern the viscosity in a 2% aqueous solution at 20°C.

Designation Cellulose ether

A ethylhydroxyethylcellulose which had been hydrophobically modified with nonyl phenyl groups, cloud point 52°C, viscosity

7,500 mPa»s

B cellulose ether according to A, whose chain had been shortened, cloud point 57°C, visco¬ sity 460° mPa»s

C carboxymethylcellulose, viscosity 10 mPa»s,

(FINNFIX 10)

D hydroxyethylcellulose, viscosity 8,000 mPa*s

E hydroxyethylcellulose, viscosity 400 mPa»s

I ethylethylhydroxyethylcellulose, cloud point

65°C, viscosity 1,230 mPa»s

II ethylhydroxyethylcellulose, cloud point 65°C, viscosity 300 mPa»s

III ethylhydroxyethylcellulose, cloud point 69°C, viscosity 5,000 mPa»s

IV ethylhydroxyethylcellulose, cloud point 69°C, viscosity 10,000 mPa»s

V ethylhydroxyethylcellulose, cloud point 69°C, viscosity 80,000 mPa«s

VI methylhydroxypropylcellulose, cloud point

57°C, viscosity 400 mPa»s

The various compositions were heated and their visco¬ sities were measured. The following results were obtained.

Test Ether Bohlin cs-viscosity 4 s^"1. mPa»s

30°C 40°C 50°C 60°C

A A 4460 4337 4871 4093

B B 2748 3199 3833 3136

C C 4667 4744 4908 5124

D D 3830 3795 3779 3639

E E 5804 5692 5412 4800

1 I 3621 4531 6094 5903

2 II 4572 6250 7855 7047

3 III 4186 5045 7398 7368

4 IV 4702 5390 6888 6190

5 V 5480 6110 6550 6750

6 VI 3860 4290 4920 4820

As appears from the results, the viscosity of the coating slip compositions according to the invention, after application, increased as the temperature was increased, whereas the coating slip compositions produced according to prior-art technique presented merely insignificant viscosity increases or even considerable viscosity decreases.

Example 2

A number of coating slip compositions having a dry solids content of 65% by weight, intended for the coating of paper, were produced based on the following recipe. 100 parts by weight calcium carbonate 10 parts by weight styrene-butadiene latex 0.6-1.1 parts by weight cellulose ether (the amount adjusted to give a viscosity according to Brookfield 100 of about 1100 mPa»s) balance water

The type of cellulose ether appears from the follow¬ ing Table. The various compositions were heated and their viscosity was measured. The following results were obtained. Test Ether Bohlin CS-viscosity 4 s^"1, mPa•s

30°C 40°C 50°C 60°C

F A 3449 3389 3865 4919

G C 3030 3011 3053 3220

H E 3101 2891 2802 2714

6 I 3254 3339 3730 5630

7 II 2572 2903 4222 7224

As appears from the results, the compositions accord¬ ing to the invention had a better development of the visco¬ sity when increasing the temperature than that of the com¬ parison compositions.

Example 3

Three different coating slip compositions having a dry solids content of 65% by weight and a viscosity (Brook- field 100) of about 1,500 mPa»s were produced. They were composed as follows.

Ingredient Formulation, parts by weight

1 2 3

Calcium carbonate 80 80 80

Kaolin 20 20 20

Latex, styrene-butadiene 10 10 10

Cellulose ether, type A 0.4

Cellulose ether, type C 0.65

Cellulose ether, type I 0.45

Water balance balance balance

A composition in an amount of 24 g was weighed in thin-walled aluminium dishes and were levelled such that the surfaces, through which evaporation of water could take place, were of the same size. The various samples were then dried in a heating cabinet at 105^CC and the change in weight was measured every 15th minute. The evaporation of water at the time 0 was determined as the average evaporation of water during the first 15 min of heating of the composition from 25°C to the final temperature 105°C. The following results were obtained.

Formulation Drying rate, g H₂0/min, time

0 15 30 60

1 0.033 0.045 0.040 0.41 2 0.031 0.038 0.033 0.033 3 0.034 0.044 0.043 0.42

From the results appears that the composition accord¬ ing to the invention, which have a higher viscosity than the comparison compositions at higher temperatures, nevertheless have the same evaporation of water or even better.

Example 4

Two coating slip compositions having a dry solids content of 65% by weight were produced, having the following composition.

Formulation, parts by weight

1 2

Calcium carbonate 100 100 Sodium polyacrylate 0.025 0.025 Cellulose ether C 0.4 Cellulose ether II 0.4 Styrene-butadiene 10 10 latex

The viscosities of the coating slip compositions were measured at 50°C, 53°C, 56°C, 59°C and 62°C according to Bohlin CS 25 s^' The following results were obtained. Temperature, °C Viscosity, mPa«s, formulation

1 2

50 380 1 250 53 390 1 630 56 400 2 070 59 410 2 330 62 420 2 290

From the results appears that the viscosity increase at the elevated temperatures was essentially higher for the coating slip composition according to the invention than for the comparison composition.

Claims

1. Use of a water-soluble nonionic alkylhydroxyalkyl¬ cellulose, which contains alkyl groups having 1-3 carbon atoms and hydroxyalkyl groups having 2-3 carbon atoms, but which is free from hydrophobically modified hydrocarbon groups having at least 4 carbon atoms, the cellulose ether having a cloud temperature in the range from 35 to 80°C, as thickening agent in aqueous compositions for coating cellu- lose-based two-dimensional products.

2. Use as claimed in claim 1, wherein the cellulose ether consists of an ethylhydroxyethylcellulose.

3. Use as claimed in claim 1, wherein the cellulose ether consists of a methylethylhydroxyethylcellulose.

4. Use as claimed in claim 1, 2 or 3, wherein the cellu¬ lose ether has a cloud point in the range from 45 to 70°, and a viscosity of 10-10,000 mPa»s in a 2% aqueous solution at 20°C.

5. An aqueous composition for coating a cellulose-based two-dimensional product containing a binder, characterised in that it contains a water-soluble nonionic alkylhydroxy¬ alkylcellulose, which contains alkyl groups having 1-3 car¬ bon atoms and hydroxyalkyl groups having 2-3 carbon atoms, but which is free from hydrophobically modified hydrocarbon groups having at least 4 carbon atoms, the alkylhydroxy¬ alkylcellulose having a cloud point in the range from 35 to 80°C.

6. The composition as claimed in claim 5 for application of a layer of a coating slip, characterised in that it contains

0.05-3% by weight of the water-soluble nonionic alkyl¬ hydroxyalkylcellulose,

5-30% by weight binder, and

5-65% by weight pigment the composition having a Brookfield viscosity from 100 to

2,500 mPa«s and a dry solids content from 20 to 70% by weight. 7. The composition as claimed in claim 6, characterised in that it contains, based on the dry solids content, the following ingredients

0.05-5% by weight of the water-soluble nonionic alkylhydroxyalkylcellulose

7-13% by weight latex, 0-7% by weight secondary binder, 0.1-2% by weight dispersing agent, 0-2% by weight protective colloid, and 70-90% by weight pigment.

8. The composition as claimed in claim 7, characterised in that it has a dry solid content of 55-70% by weight, and that the latex consists at least partially of a styrene- butadiene latex or an acrylate latex, and that the pigment consists at least partially of calcium carbonate or kaolin.

9. The composition as claimed any one of claims 5-8, characterised in that the alkylhydroxyalkylcellulose is a methylethylhydroxyethylcellulose or an ethylhydroxyethyl¬ cellulose having a cloud point in the range from 45 to 70°C and a viscosity of 10-10,000 mPa»s measured in a 2% solution at a temperature of 20°C.

10. A method for producing a coated cellulose-based two- dimensional product, characterised in that a) an aqueous composition according to any one of claims 5-9 is applied to the cellulose-based two-dimensional product at a temperature below the cloud temperature of the alkylhydroxyalkylcellulose, and b) the cellulose-based product coated with the composi¬ tion is dried during heating, and c) if desired, said product is calendered.