CA2085348C - Paper, paperboard and cardboard internal sizing process - Google Patents

Paper, paperboard and cardboard internal sizing process Download PDF

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Publication number
CA2085348C
CA2085348C CA002085348A CA2085348A CA2085348C CA 2085348 C CA2085348 C CA 2085348C CA 002085348 A CA002085348 A CA 002085348A CA 2085348 A CA2085348 A CA 2085348A CA 2085348 C CA2085348 C CA 2085348C
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Prior art keywords
units
paper
fixing agent
vinyl
polymerized
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CA002085348A
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French (fr)
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CA2085348A1 (en
Inventor
Michael Kroener
Claudia Nilz
Norbert Sendhoff
Andreas Stange
Arnold De Clercq
Ulrich Riebeling
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Sanitary Thin Papers (AREA)
  • Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)

Abstract

According to a paper, paperboard and cardboard internal sizing process, resin size is used, as well as cationic polymers containing polymerized vinylamine units as fixing agents for the resin size.

Description

a 2~~"~~~-i~ 0.~. 0050/41956 Engine sizing of caper, board and cardboard The present invention relates to a process for the engine sizing of paper, board and cardboard using d a cationic polymer which contains polymer-i ze an resin s ized vinylamine units as a fixing agent.

;., U.S. Patent 4,421,602 discloses partially hydro-"' lyzed homopolymers of N-vinylformamide which contain N-vinylformamide and vinylamine units. They are used as .

retention and drainage aids and flocculants in paper-making.

EP-A-0 216 387 discloses that copolymers of from 95 to 10 mol % of N-vinylformamide and from 5 to 90 mol %

of an ethylenically unsaturated monomer from the group consisting of vinyl acetate, vinyl propionate, the C1-C4-alkyl vinyl ethers, N-vinylpyrrolidone, the esters, nitriles and amides of acrylic acid and methacrylic acid in partially or completely hydrolyzed form, in which up 100 mol % of the formyl groups have been eliminated to from the copolymer, are added in amounts of from 0.1 to . 20 5% by weight, based on dry fibers, to the paper stock prior to sheet formation, as wet strength and dry strength agents for paper.

> German Laid-Open Application DOS 3,203,189 .;..i . discloses sizes based on hydrophobic, cellulose-reactive sizing materials and fixing and sizing accelerators consisting of polymers which contain primary, secondary or tertiary amino groups and/or quaternary ammonium groups bonded directly or via side chains. These cationic polymers include hydrolyzed polymers of N-vinylformamide and partially hydrolyzed copolymers of N-vinylacetamide and vinyl acetate. According to the German Laid-Open Application, hydrophobic, cellulose-reactive sizing ~~~ materials are preferably alkylketene dimers, anhydrides,.

such as rosin anhydride, and isocyanates.

The most well known engine size based on natural products is resin size. This is a compound which is not reactive toward cellulose fibers and is precipitated onto CA 02085348 2002-~04-29 I

the- cellulose fibers in the paper stock with the addition of fixing agents. Examples of suitable fixing agents are aluminum sulfate or, according to German Published Application DAS 1,070,916 and European Patent 0,187,666, cationic dicyanodiamide resins. While the efficiency of the cationic dicyanodiamide resins is unsatisfactory, aluminum sulfate and alum have the disadvantage that calcium carbonate cannot be used as a filler in their presence and the papers obtainable in this manner are not sufficiently resistant to aging owing to the fact that the process is carried out at acidic pH.
The present invention provides a process for the engine sizing of paper, board and cardboard with resin size, in which sizing can be carried out at neutral pH and in which papers resistant to aging are obtained.
According to the invention, there is provided a process for the engine sizing of paper, board and cardboard using resin size and a fixing agent for fixing the resin size to the cellulose fibers, if the fixing agent used is a cationic polymer which contains polymerized vinylamine units.
In the present context, resin sizes are the products conventionally used for the engine sizing of paper and based on natural substances, for example resin sizes consisting of hydrogenated rosin, tallow resin sizes, reinforced resin sizes, dry resin sizes or emul-sions rich in free resin. These products are nonreactive resin sizes which result in virtually no sizing of paper when used alone for engine sizing but always have to be used together with a fixing agent. Suitable resin sizes are described in, for example, Papier 43 (5), (1989), 188-192. As in known processes for the engine sizing of paper, in the present process too resin size is used in an amount of from about 1 to 4, preferably from 1.5 to 3, ~ by weight, based on dry paper stock.
According to the invention, the engine sizing of - 3 - O.Z. 0050/41956 paper is carried out in the presence of small amounts of aluminum sulfate and/or alum, using a cationic polymer which contains polymerized vinylamine units. Aluminum sulfate and alum are used in amounts of < 5, preferably from 2 to 3, ~ by weight, as a precipitating agent for resin size. The cationic polymers surprisingly act as fixing agents for nonreactive resin size. Polymers of this type are disclosed, for example, in U.S. Patent 4,421,602 and EP-A-0 216 387, which were mentioned in connection with the prior art. They are prepared by hydrolyzing homo- and copolymers containing polymerized N-vinylamides.
Such polymers contain the following typical structures:
_CH 2_ I H_ R/ \C\ ( Z ) where R and R1 are each H or C1-C6-alkyl.
For the preparation of compounds which contain ' exclusively structural units of the formula I, for example, N-vinylformamide, N-vinylacetamide, N-vinyl-N
methylformamide, N-vinylpropionamide or N-vinylbutyramide is polymerized. The structure N (ZZ) /\
R H
where R is H or C1-Cfi-alkyl is formed from the compounds containing structural elements of the formula Z by hydrolysis using an acid, eg. hydrochloric acid, sulfuric . acid or phosphoric acid, or in the presence of a base, such as sodiumhydroxide solution or potassium hydroxide solution, with elimination of the group -CO-R1.
Zn the case of 100% hydrolysis of all units of the structure Z in the polymer, polyvinylamines are -. - 4 - O.Z. 0050/41956 obtained. If only partial hydrolysis is carried out, the polymers prepared from the N-vinylamides contain units of the structures I and II. The compound of the formula CHO
/ (III) CH = CH-H\
H
ie. N-vinylformamide, is preferably used as the N-vinyl-amide. Partially hydrolyzed homopolymers of the compound III are disclosed in the abovementioned U.S. Patent 4,421,602. The degree of hydrolysis may be from 0.1 to 100%. The preferred polymers captaining polymerized vinylamine units include compounds which are obtainable by copolymerization of (a) from 1 to 99, preferably from 10 to 90, mol % of N-vinylformamide and (b) from 99 to 1 mol % of monoethylenically unsaturated monomers from the group consisting of vinyl acetate, vinyl propionate, the C1-C,-alkyl vinyl ethers, N
vinylpyrrolidone, the esters, nitriles, amides, N
alkylamides and sulfo-carrying N-alkylamides of acrylic acid and methacrylic acid and mixtures of these monomers and subsequent hydrolysis of the amide groups of the structural units I of the polymers to form amino groups of the structure II. The degree of hydrolysis of the polymerized N-vinylformamide units is from Ø1 to 100%, preferably not less than 10%.
Such copolymers are described in EP-A-0 216 387.
In addition to N-vinylformamide, for example, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacet-amide, N-vinylpropionamide or N-vinylbutyramide can be used as a monomer of component (a). In the hydrolysis of copolymers of N-vinylformamide and vinyl acetate or vinyl propionate, it is also possible, depending on the reac-tion conditions, to hydrolyze the polymerized monomer units (b), so that, in the case of the last-mentioned 2n~~~;~9 ~
.,.
- 5 - O.Z. 0050/41956 comonomers, the copolymers then additionally contain, for example, polymerized vinyl alcohol units. The degree of hydrolysis of the acetyl and/or propionyl groups in the polymerized units (b) of the copolymers may be from 0.1 to I00~.
The homo- and copolymers containing polymerized vinylamine units have K values of from 5 to 300, prefer-ably from 15 to 150. Polyvinylamines and hydrolyzed copolymers of N-vinylformamide having K values of from 20 to 115 are particularly preferred.
The cationic polymers containing polymerized vinylamine units are water-soluble. For engine sizing, they are added directly to the paper stock or can be added to the paper stock in the form of a mixture with the resin size. In the case of separate metering of the polymer and resin size, it is unimportant whether the resin size or the cationic polymer is added first to the paper stock because adequate mixing of the components always takes place in the paper stock. From 1 to 100, preferably from 5 to 30, parts by weight of one or more cationic polymers which contain polymerized vinylamine units are used per 100 parts by weight of resin size.
Suitable fibers for the preparation of the pulps are all conventional qualities, for example mechanical pulp, bleached and unbleached chemical pulp and paper stocks obtained from all annual plants. Mechanical pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure-ground.
pulp, semi-chemical pulp, high-yield chemical pulp and refiner mechanical pulp (RMP). Examples of suitable chemical pulps are sulfate, sulfite and soda pulps. The unbleached chemical pulps, which are also referred to as unbleached kraft pulps, are preferably used. Suitable annual plants for the preparation of paper stocks are, for example, rice, wheat, sugar cane and kenaf. Waste paper, either alone or as a mixture with other fibers, is also used for the preparation of the pulps. For the --~ - 6 - 0. Z . 0050/41956 production of paper, board and cardboard, the pulps' are mixed with resin size and, as fixing agents, one or more polymers to be used according to the invention, and are drained on a wire.of a paper machine in a known manner.

The consistency of the pulps is from 0.1 to 1.5%
by weight and their pH is not snore than 8, preferably from 6 to 7.5.

In the Examples which follow, parts and per-centages are by weight. The K values were determined according to H. Fikentscher, Cellulose-Chemie 18 (1932), 48-64 and 71-74, in 5% strength aqueous sodium chloride solution at 25C and at a polymer concentration of 1% by Weight. The .quality'of sizing was determined with the aid of the Cobb value according to DIN 53,132 and the ink flotation test (50% strike-through). To characterize the sizing, the preparation take-up was also determined.
For this purpose, a paper strip ( 80 cm x 10 cm) was drawn through a laboratory size press to constant contact pressure and a speed of 10 m/min. The test liquid used was tap water. The preparation take-up was calculated ;a from the weight increase as follows:

(Weight after size press -Weight before size press ) x 100 Preparation take-up = -Weight of absolutely dry sample The following starting materials were used:
Size 1 50% strength low-viscosity resin soap prepared from chemically reinforced natural~resins having a total resin acid number of 170, a free resin content of about 2% and a Brookfield viscosity of 1,000 mPa.s at 20°C and 20 rpm.
Fixing agent 1 lI% strength aqueous solution of a copolymer which contained 98% of vinylaanine units and 2% of N
vinylformamide units and had a K value of 87. The pH of the aqueous solution was 3.5.

2~t~~'~~,~~8 O.Z. 0050/41956 Fixing agent 2 12% strength aqueous solution (pH 3.5) of a copolymer which contained 68% of vinylamine units, 2% of N-vinylformamide units, 25% of vinyl alcohol units and 5%
of vinyl acetate units and had a K value of 105.
Fixing agent 3 17% strength aqueous solution of a copolymer which contained 4S% of vinylamine units and 55% of N-vinylformamide units and had a K value,of 87. The pH of the aqueous solution was 3.5.
EXAMPLES
A paper stock was prepared from 100% bleached birch sulfate pulg with the addition of 40% of chalk.
The freeness was 35°SR (Schopper-Riegler) . 1.5% by weight of the size, 3% by weight of alum and then 0.1% by weight of one of the fixing agents stated in Tables 1 and 2 were added to the paper stock, the percentages being based on the solids content. The pH of the stock ;remained un-changed at 7. In all Examples, 0.3% of a commercial weakly cationic polyacrylamide having a K value of 130 was also added as a retention aid to the paper stock, after which sheets having a basis weight of 100 g/m2 were formed on a Rapid-Kathen sheet former. The sheets were each dried on a steam-heated drying cylinder at 90°C to a residual moisture content of from 6 to 10%.
In all Examples, the preparation take-up, the Cobb value and the ink flotation time were determined immediately after drying. These results are summarized in Table 1. The sheets were then stored for one day at 23°C and' at a relative humidity of 50%. The preparation take-up, the Cobb value and the ink flotation time were then determined. The results obtained are shown in Table 2.
COMPARATIVE EXAMPLE
Example 1 was repeated, with the sole exception that, instead of 0.1% by weight of fixing agent 1, only 3% by weight of alum were used as a fixing agent and 2~?~~~~'.8 - 8 - O.Z. 0050/41956 precipitating agent. The pH of the pulp was 7. ~ The results obtained are shown in Tables 1 and 2.

Immediate sizing S Example Fixing Preparation Cobb value Ink flotation agent take-up ($) 60 " time (min}
1 1 21.1 31 >60 2 2 22.S 51 30 3 3 21.2 41 >60 Comparative Example ,1 ~ alum 30.3 46 5 Sizing afteraging Example Fixing Preparation Cobb valueInk flotation agent take-up (~) , 60 " time (min) 1 1 18.5 46 >60 2 2 21.5 49 >30 3 3 17.9 41 >60 Comparative Example 1 1 31.2 64 1 r

Claims (6)

CLAIMS:
1. A process for the engine sizing of paper, board and cardboard using resin size and a fixing agent for fixing the resin size to the cellulose fibers, wherein the fixing agent used is a cationic polymer which con-tains polymerized vinylamine units.
2. A process as claimed in claim 1, wherein the fixing agent used is a hydrolyzed homopolymer of N-vinyl-formamide having a degree of hydrolysis of from 0.1 to 100%.
3. A process as claimed in claim 1, wherein the fixing agent used is a hydrolyzed copolymer of N-vinyl-formamide which contains, as polymerized units, not more than 99 mol % of ethylenically unsaturated monomers from the group consisting of vinyl acetate, vinyl propionate, the C1-C4-alkyl vinyl ethers, N-vinylpyrrolidone, the esters, nitriles and amides of acrylic acid and meth-acrylic acid and in which the degree of hydrolysis of the polymerized N-vinylformamide units is from 0.1 to 100%.
4. A process as claimed in claim 1 or 2 or 3, wherein the fixing agent used is a hydrolyzed polymer which is obtained by polymerizing (a) from 100 to 10 mol % of N-vinylformamide and (b) from 0 to 90 mol % of vinyl acetate ar vinyl propionate and subsequently eliminating from 0.1 to 100% of the formyl groups from the polymerized units (a) and, if required, from 0.1 to 100% of the acetyl or propionyl groups from the polymerized units (b) of the copolymer.
5. A process as claimed in claim 1 or 2 or 3 or 4, wherein from 10 to 300 parts by weight of one or more cationic polymers are used per 100 parts by weight of resin size.
6. Use of a cationic polymer which contains polymer-ized vinylamine units as a fixing agent for resin size in the engine sizing of paper, board and cardboard.
CA002085348A 1990-10-15 1991-10-04 Paper, paperboard and cardboard internal sizing process Expired - Fee Related CA2085348C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DEP4032660.8 1990-10-15
DE4032660A DE4032660A1 (en) 1990-10-15 1990-10-15 METHOD FOR SIZING PAPER, CARDBOARD AND CARDBOARD
PCT/EP1991/001894 WO1992007141A2 (en) 1990-10-15 1991-10-04 Paper, paperboard and cardboard internal sizing process

Publications (2)

Publication Number Publication Date
CA2085348A1 CA2085348A1 (en) 1992-04-16
CA2085348C true CA2085348C (en) 2005-06-14

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ID=6416303

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CA002085348A Expired - Fee Related CA2085348C (en) 1990-10-15 1991-10-04 Paper, paperboard and cardboard internal sizing process

Country Status (10)

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EP (1) EP0553135B1 (en)
JP (1) JP3176620B2 (en)
AT (1) ATE116394T1 (en)
AU (1) AU8646891A (en)
CA (1) CA2085348C (en)
DE (2) DE4032660A1 (en)
ES (1) ES2067249T3 (en)
FI (1) FI97405C (en)
NZ (1) NZ240196A (en)
WO (1) WO1992007141A2 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5280077A (en) * 1992-07-14 1994-01-18 Air Products And Chemicals, Inc. Process for the synthesis of oligomeric vinylamines
US5519093A (en) * 1994-05-11 1996-05-21 Air Products And Chemicals, Inc. Synthesis of amine functional co-and terpolymers
US6273998B1 (en) 1994-08-16 2001-08-14 Betzdearborn Inc. Production of paper and paperboard
DE19753212A1 (en) * 1997-12-01 1999-06-02 Basf Ag Process for mass sizing paper, cardboard and cardboard
DE10237913A1 (en) * 2002-08-14 2004-02-26 Basf Ag Production of cardboard for packaging liquids by treating pulp with a sizing agent and a retention aid comprises adding a cationic polymer to the pulp
JP2005171411A (en) * 2003-12-10 2005-06-30 Seiko Pmc Corp Filler-containing paper and method for producing filler-containing paper

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE23584T1 (en) * 1982-08-25 1986-11-15 Ciba Geigy Ag PROCESS FOR SIZING PAPER WITH ANIONIC, HYDROPHOBIC SIZES AND CATIONIC RETENTION AGENTS.
DE3534273A1 (en) * 1985-09-26 1987-04-02 Basf Ag METHOD FOR PRODUCING VINYLAMINE UNITS CONTAINING WATER-SOLUBLE COPOLYMERISATS AND THE USE THEREOF AS WET AND DRY-FASTENING AGENTS FOR PAPER
CA1283748C (en) * 1986-06-25 1991-04-30 Takaharu Itagaki Vinylamine copolymer, flocculating agent and paper strength increasingagent using the same, as well as process for producing the same
GB8806432D0 (en) * 1988-03-18 1988-04-20 Albright & Wilson Paper sizing methods & compositions
DE4001045A1 (en) * 1990-01-16 1991-07-18 Basf Ag Paper, paste-board and cardboard prodn. - by draining pulp contg. retention agent and as fixing agent, min. 60 per cent-hydrolysed homo- or copolymer of N-vinyl-formamide

Also Published As

Publication number Publication date
EP0553135B1 (en) 1994-12-28
FI97405B (en) 1996-08-30
DE4032660A1 (en) 1992-04-16
FI931642L (en) 1993-04-13
DE59104096D1 (en) 1995-02-09
EP0553135A1 (en) 1993-08-04
FI931642A0 (en) 1993-04-13
AU8646891A (en) 1992-05-20
CA2085348A1 (en) 1992-04-16
NZ240196A (en) 1993-10-26
JP3176620B2 (en) 2001-06-18
ATE116394T1 (en) 1995-01-15
JPH06501993A (en) 1994-03-03
WO1992007141A2 (en) 1992-04-30
FI97405C (en) 1996-12-10
WO1992007141A3 (en) 1992-06-11
ES2067249T3 (en) 1995-03-16

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