EP0375244A2 - Preparation of a wallpaper pigmented ground coat - Google Patents

Preparation of a wallpaper pigmented ground coat Download PDF

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Publication number
EP0375244A2
EP0375244A2 EP19890312937 EP89312937A EP0375244A2 EP 0375244 A2 EP0375244 A2 EP 0375244A2 EP 19890312937 EP19890312937 EP 19890312937 EP 89312937 A EP89312937 A EP 89312937A EP 0375244 A2 EP0375244 A2 EP 0375244A2
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EP
European Patent Office
Prior art keywords
weight
wallpaper
emulsion
copolymer emulsion
epoxy silane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19890312937
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German (de)
French (fr)
Other versions
EP0375244B1 (en
EP0375244A3 (en
Inventor
Razmik Baghdassar-Zadeh Boodaghians
David Bretland Farmer
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Unilever PLC
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Unilever PLC
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Application filed by Unilever PLC filed Critical Unilever PLC
Priority to AT89312937T priority Critical patent/ATE102669T1/en
Publication of EP0375244A2 publication Critical patent/EP0375244A2/en
Publication of EP0375244A3 publication Critical patent/EP0375244A3/en
Application granted granted Critical
Publication of EP0375244B1 publication Critical patent/EP0375244B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters

Definitions

  • This invention relates to the use of aqueous emulsions in pigmented wallpaper ground coats.
  • aqueous emulsions are based on vinyl alkanoate copolymers, usually vinyl acetate/ethylene copolymers.
  • Pigmented wallpaper ground coats are applied on one side of a cellulosic wallpaper substrate. This side is then printed and will form the exposed surface when adhered to a wall.
  • the wet rub resistance of the exposed surface is important because it allows the printed surface to be washed without eroding the decorative appearance.
  • the invention provides for the use in a wallpaper ground coat of a copolymer emulsion latex having a solids contents of about 20% to about 70% by weight, preferably from about 40% to about 60%, wherein vinyl C1 to C13 alkanoate forms at least about 40% by weight of the monomer charge characterised in that
  • vinyl acetate is the preferred vinyl alkanoate monomer because of its availability, cost and known reactivity
  • other vinyl esters within the class defined are usable in particular vinyl formate, propionate, butyrate, isobutyrate, valerate, 2-ethyl hexanoate, isooctanoate, nonanoate, decanoate, pivalate and versatate.
  • a preferred comonomer is ethylene but other ethylenic hydrocarbons, for example propylene, butylene and isobutene and higher alpha-olefins, are usable.
  • the copolymer may contain minor monomer components added to provide specific benefits, examples are sodium vinyl sulphonate, acrylic acid, methacrylic acid, acrylamide, hydroxy functional acrylates, vinyl silanes and vinyl halides.
  • a favoured comonomer is a polyethylenically unsaturated compound selected from triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, divinyl benzene and diallyl phthalate.
  • the epoxy silane used is preferably a gamma glycidoxy silane, having the formula x-Si(OR)3 whre X is an alkyl group containing a reactive expoxy moiety and R, which may be the same or different, is hydrogen, C1 to C4 alkyl radicals with not more than two of the radicals being hydrogen.
  • X is an alkyl group containing a reactive expoxy moiety
  • R which may be the same or different, is hydrogen, C1 to C4 alkyl radicals with not more than two of the radicals being hydrogen.
  • Examples are gamma glycidoxy propyl trimethoxy silane and gamma glycidoxy propyl methoxy diethoxy silane.
  • stabilising surfactant having an alkylene moeity examples include oleyl propanol amide sulphosuccinate obtained from Witco of USA under the trade name Emcol 8300 and the potassium salt of the sulphonation product of oleic acid obtainable from Lankro Chemcials of Manchester, England under the trade name Lankropol OPA.
  • the coat composition was coated onto a wallpaper at a level of 25g/m2 and dried for 2 minutes at 120°C. It was then equilibrated overnight at 20°C and 65% RH. The coated wallpaper was then callendered twice at 50 to 55°C under a pressure of 200 lbs/sq in and then allowed to equilibrate overnight at 20°C and 65% RH before testing.
  • Timperley testing machine fitted with a felt pad was used with a soft soap solution and set to operate at 120 ⁇ 10 strokes/minute. All groundcoats were tested to 150 rubs and visually graded for coating abrasion.
  • the surfactant solution comprising a 37% aq solution of Emcol K8300 (87.7g), 30% aq solution of Aerosol A102 (61.5g) and ammonium persulphate (4.3g, initial charge) dissolved in deionised water (1038g) was prepared and charged to a 4 litre pressure vessel heated to 38°C. At 38°C the reactor was purged twice with nitrogen, once with ethylene and pressurised with ethylene to 800 psi with stirring. The temperature was adjusted to 75°C while 10% of the monomer phase was pumped to the reactor.
  • reaction mass was held at 75°C for 30 minutes then the continuous additions of persulphate solution (5.3g in 300g of deionised water) and the remainder (90%) of the monomer phase were started.
  • persulphate solution was added over 6.5 hours and the monomer phase over 6.0 hours.
  • the pressure was maintained at 800 psi until the desired quantity of ethylene has been reacted, this was after 3.5 hours from start of continuous additions.
  • reaction mass was held at 80°C for 30 minutes and the contents of the reactor then cooled to 40°C followed by pumping of finishing off stage (4.6g of each in 50g of deionised water) to the reactor, in separate streams, over 30 minutes.
  • finishing off stage 4g of each in 50g of deionised water
  • the contents of the reactor then cooled to 25°C and discharged to a degassing tank.
  • Ammonia solution was used to adjust the pH of the emulsion latex to 8 then post-reacted with 1.0% epoxy silane while stirring.
  • the emulsion had a solids content of 50%.
  • Example 1-4 which contain acrylic acid as a functional comonomer, all show an improvement in scrub resistance on post-addition of epoxy silane. However results for example 5 show an improvement and here the acrylic acid is absent. It is however, regarded as essential that the polymerisation is performed in the presence of an effective amount of stabilising surfactant having a C14 to C20 alkylene moiety.
  • a surfactant solution comprising a 37% aqueous solution of Emcol K8300 (15.7g), 31% aqueous solution of Aerosol A102 (11.0g) and ammonium persulphate (0.8g) dissolved in distilled water (180g) was charged to a 1 litre glass reactor, purged twice with nitrogen and heated to 75°C with stirring.
  • a monomer mix comprising: vinyl acetate 200 g butyl acrylate 50 g acrylic acid 2.5 g diallyl maleate 0.5 g had been previously prepared and 10% was added to the reactor when the temperature reached 60 to 65°C. When the reactor temperature reached 75°C it was held at that temperature for 45 minutes.
  • Ammonia solution was used to adjust the pH of the emulsion latex to 8 then post-reacted with the epoxy silane of Example I while stirring.
  • the emulsion had a solids content of 50%.
  • Example 6 The procedure of Example 6 was repeated but using a base monomer charge of: vinyl acetate 80% butyl acrylate 20% and a functional monomer charge: acrylic acid 0.5 pphm diallyl maleate 0.2 pphm sodium vinyl sulphonate 1.0 pphm
  • Example 6 and 7 which contain acrylic acid as a functional comonomer, all show an improvement in scrub resistance on post-addition of epoxy silane, (Table 1). However, results for example 8 also shows an improvement and here the acrylic acid is absent. It is however regarded as essential that the polymerisation is performed in the presence of an effective amount of stabilising surfactant having a C14 to C20 alkylene moiety. This is demonstrated in example 9.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Lubricants (AREA)
  • Paper (AREA)
  • Colloid Chemistry (AREA)

Abstract

The wet rub resistance of a pigmented wallpaper ground coat is improved by using a polymer emulsion prepared by pressure reaction in the presence of a stabilising surfactant containing a C14 to C20 alkylene moiety and then post reacted with an epoxy silane.

Description

    FIELD OF THE INVENTION:
  • This invention relates to the use of aqueous emulsions in pigmented wallpaper ground coats. These aqueous emulsions are based on vinyl alkanoate copolymers, usually vinyl acetate/ethylene copolymers.
    • BACKGROUND TO THE INVENTION:
  • Pigmented wallpaper ground coats are applied on one side of a cellulosic wallpaper substrate. This side is then printed and will form the exposed surface when adhered to a wall. The wet rub resistance of the exposed surface is important because it allows the printed surface to be washed without eroding the decorative appearance.
    • GENERAL DESCRIPTION OF THE INVENTION:
  • The invention provides for the use in a wallpaper ground coat of a copolymer emulsion latex having a solids contents of about 20% to about 70% by weight, preferably from about 40% to about 60%, wherein vinyl C1 to C13 alkanoate forms at least about 40% by weight of the monomer charge characterised in that
    • i) the polymerisation is performed in the presence of an effective amount of a stabilising surfactant having a C14 to C20 alkylene moiety, and
    • ii) the polymerised emulsion is reacted with an effective amount, preferably about 0.1% to about 3% by weight of the emulsion of an epoxy silane material. The stabilising surfactant is preferably present in an amount of from about 1% to about 10%, preferably 2% to 8%, by weight of the copolymerisable monomers.
  • Although vinyl acetate is the preferred vinyl alkanoate monomer because of its availability, cost and known reactivity, other vinyl esters within the class defined are usable in particular vinyl formate, propionate, butyrate, isobutyrate, valerate, 2-ethyl hexanoate, isooctanoate, nonanoate, decanoate, pivalate and versatate.
  • A preferred comonomer is ethylene but other ethylenic hydrocarbons, for example propylene, butylene and isobutene and higher alpha-olefins, are usable. Alkyl (C2 to C8) acrylates, eg. ethyl, butyl and 2-ethyl hexyl acrylate, are also preferred comonomers.
  • Optionally the copolymer may contain minor monomer components added to provide specific benefits, examples are sodium vinyl sulphonate, acrylic acid, methacrylic acid, acrylamide, hydroxy functional acrylates, vinyl silanes and vinyl halides. A favoured comonomer is a polyethylenically unsaturated compound selected from triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, divinyl benzene and diallyl phthalate.
  • The epoxy silane used is preferably a gamma glycidoxy silane, having the formula x-Si(OR)₃ whre X is an alkyl group containing a reactive expoxy moiety and R, which may be the same or different, is hydrogen, C1 to C4 alkyl radicals with not more than two of the radicals being hydrogen. Examples are gamma glycidoxy propyl trimethoxy silane and gamma glycidoxy propyl methoxy diethoxy silane.
  • Examples of the stabilising surfactant having an alkylene moeity are oleyl propanol amide sulphosuccinate obtained from Witco of USA under the trade name Emcol 8300 and the potassium salt of the sulphonation product of oleic acid obtainable from Lankro Chemcials of Manchester, England under the trade name Lankropol OPA.
  • Methods for preparing the copolymer emulsions of the invention are well characterised in the literature. Polymer Synthesis (vols I and III) by Sandler & Karo (Academic Press 1974) and Preparative Methods of Polymer Chemistry (2nd Ed) by Sorenson and Campbell (Interscience 1968) provide preparative information. Methoden der Organischen Chemie (Houben-Wey) Band XIV published by George Tieme Verlag Stuttgart (1961) also provides preparative descriptions.
    • TEST METHOD:
  • Wet scrub resistance was measured by formulating the aqueous emulsion into the wallpaper ground coat composition (parts by dry weight).
    Emulsion 20 parts
    Clay 100 *
    Water retention aid 0.5 **
    Dispersant 0.3 ***
    Sodium hydroxide to give 45% solids 0.15
    * Obtainable as SPS clay from English China Clay Ltd of St Austell England.
    ** Obtainable as Finnfix FF5 from Finn Forest Chemicals of Cheam, England
    *** Obtainable as Dispex N40 from Allied Colloids Ltd of Bradford, England.
  • The coat composition was coated onto a wallpaper at a level of 25g/m² and dried for 2 minutes at 120°C. It was then equilibrated overnight at 20°C and 65% RH. The coated wallpaper was then callendered twice at 50 to 55°C under a pressure of 200 lbs/sq in and then allowed to equilibrate overnight at 20°C and 65% RH before testing.
  • In method A a Timperley testing machine fitted with a felt pad was used with a soft soap solution and set to operate at 120 ± 10 strokes/minute. All groundcoats were tested to 150 rubs and visually graded for coating abrasion.
  • In method B a wet abrasion scrub tester (Sheen Instruments Ltd of Teddington England) fitted with a hogs hair brush was used with a soft soap solution. Groundcoats were tested to 500 scrubs and again visually graded for coating abrasion.
    VS - very slight, ie. best resistance
    S - slight
    M - moderate
    H - heavy
    VH - very heavy, ie. worst resistance
    • SPECIFIC DESCRIPTION OF THE INVENTION:
  • Examples of the preparation and use of vinyl acetate copolymer emulsions will now be given to illustrate but not limit the invention.
    • EXAMPLE I
  • The components were utilised in the following percentages.
    Monomer Phase % by weight
    base monomers: Vinyl acetate 80.00
    Ethylene 20.0
    functional monomers:
    Acrylic Acid 1.0 pphm
    Diallyl Maleate 0.2 pphm
    pphm = parts per hundred of base monomer
    Surfactant System
    Emcol K8300 2.3
    Aerosol A102 1.3
    Initiator System
    Ammonium persulphate
    i) initial charge 0.3
    ii) continuous addition 0.4
    Finishing off stage
    t-butyl hydroperoxide 0.3
    Sodium metabisulphite 0.3
    Post-addition
    gamma-glycidoxypropyltrimethoxysilane 1.0
  • The surfactant solution comprising a 37% aq solution of Emcol K8300 (87.7g), 30% aq solution of Aerosol A102 (61.5g) and ammonium persulphate (4.3g, initial charge) dissolved in deionised water (1038g) was prepared and charged to a 4 litre pressure vessel heated to 38°C. At 38°C the reactor was purged twice with nitrogen, once with ethylene and pressurised with ethylene to 800 psi with stirring. The temperature was adjusted to 75°C while 10% of the monomer phase was pumped to the reactor.
  • The reaction mass was held at 75°C for 30 minutes then the continuous additions of persulphate solution (5.3g in 300g of deionised water) and the remainder (90%) of the monomer phase were started. The persulphate solution was added over 6.5 hours and the monomer phase over 6.0 hours.
  • The pressure was maintained at 800 psi until the desired quantity of ethylene has been reacted, this was after 3.5 hours from start of continuous additions.
  • After completion of all continuous addition the reaction mass was held at 80°C for 30 minutes and the contents of the reactor then cooled to 40°C followed by pumping of finishing off stage (4.6g of each in 50g of deionised water) to the reactor, in separate streams, over 30 minutes. The contents of the reactor then cooled to 25°C and discharged to a degassing tank.
  • Ammonia solution was used to adjust the pH of the emulsion latex to 8 then post-reacted with 1.0% epoxy silane while stirring. The emulsion had a solids content of 50%.
  • The product emulsion and post reacted emulsion were each tested for scrub resistance: the results are given in Table I.
    • Example 2
  • The procedure of example 1 was repeated but using a base monomer charge of:
    vinyl acetate 90%
    ethylene 10%
    and a functional monomer charge:
    acrylic acid 1.0 pphm
    diallyl maleate 0.2
    • Example 3
  • The procedure of example 1 was repeated but using a base monomer charge of:
    vinyl acetate 77%
    ethylene 23%
    and a functional monomer charge:
    acrylic acid 0.5 pphm
    diallyl maleate 0.2
    • Example 4
  • The procedure of example 1 was repeated but using a base monomer charge of:
    vinyl acetate 84%
    ethylene 16%
    and a functional monomer charge:
    acrylic acid 0.5 pphm
    diallyl maleate 0.2
  • In addition the surfactant Aerosol A102 (1.3%) was replaced by Arylan SC15 0.45% (Dodecylbenzene sulphonate ex. Lankro Chemicals, Manchester, England).
    • Example 5
  • The procedure of example 1 was repeated but using a base monomer charge of:-
    vinyl acetate 93%
    ethylene 7%
  • With no functional monomer charge, in addition the surfactant Aerosol A102 (1.3%) was replaced by Arylan SC15 (0.45%).
  • Example 1-4, which contain acrylic acid as a functional comonomer, all show an improvement in scrub resistance on post-addition of epoxy silane. However results for example 5 show an improvement and here the acrylic acid is absent. It is however, regarded as essential that the polymerisation is performed in the presence of an effective amount of stabilising surfactant having a C14 to C20 alkylene moiety.
    • Example 6
  • This example described the preparation and use of a copolymer emulsion having the composition by weight of:
    vinyl acetate 80%
    butyl acrylate 20%
    and a functional monomer charge:
    acrylic acid 1.0 pphm
    diallyl maleate 0.2
  • A surfactant solution comprising a 37% aqueous solution of Emcol K8300 (15.7g), 31% aqueous solution of Aerosol A102 (11.0g) and ammonium persulphate (0.8g) dissolved in distilled water (180g) was charged to a 1 litre glass reactor, purged twice with nitrogen and heated to 75°C with stirring. A monomer mix comprising:
    vinyl acetate 200 g
    butyl acrylate 50 g
    acrylic acid 2.5 g
    diallyl maleate 0.5 g
    had been previously prepared and 10% was added to the reactor when the temperature reached 60 to 65°C. When the reactor temperature reached 75°C it was held at that temperature for 45 minutes.
  • Then an ammonium persulphate solution (persulphate 0.95g in distilled water 30g) was added continuously over a 5 hour period and the remaining 90% of the monomer mix added over 4-5 hours. After completion of all additions the reaction was held at 75°C for 30 minutes and the contents of the reactor cooled to 40°C before adding a finishing off stage of oxidising and reducing agent.
  • Ammonia solution was used to adjust the pH of the emulsion latex to 8 then post-reacted with the epoxy silane of Example I while stirring. The emulsion had a solids content of 50%.
  • The product emulsion and post reacted emulsion were each tested for scrub resistance, the results are given in Table 1.
    • Example 7
  • The procedure of Example 6 was repeated but using a base monomer charge of:
    vinyl acetate 80%
    butyl acrylate 20%
    and a functional monomer charge:
    acrylic acid 0.5 pphm
    diallyl maleate 0.2 pphm
    sodium vinyl sulphonate 1.0 pphm
    • Example 8
  • The procedure of example 7 was repeated but omitting the functional monomers and replacing Aerosol A102 (1.3%) with Arylan SC15 (0.28%).
  • Example 6 and 7, which contain acrylic acid as a functional comonomer, all show an improvement in scrub resistance on post-addition of epoxy silane, (Table 1). However, results for example 8 also shows an improvement and here the acrylic acid is absent. It is however regarded as essential that the polymerisation is performed in the presence of an effective amount of stabilising surfactant having a C14 to C20 alkylene moiety. This is demonstrated in example 9.
    • Example 9 (comparison)
  • The procedure of example 7 was repeated but omitting the functional monomers and replacing the Emcol K8300 with further Aerosol A102. Adjustment to pH 8 with ammonia and post-addition of epoxy silane did not show any improvement in the scrub resistance over that of the base emulsion.
  • The emulsions of the invention gave improved results when incorporated in wallpaper ground coats. TABLE 1
    EXAMPLE SCRUB RESISTANCE
    PRODUCT POST REACTED
    A B A B
    1 H * VS VS
    2 * VH * M
    3 VH * S *
    4 VH * S/M *
    5 S/M S/M S S
    6 * VH * M
    7 VH * M *
    8 * H * S/M
    9** M VH M VH
    * not measured
    ** comparison
  • It is seen that post reacting the product emulsion with epoxy silane improves the scrub resistance.

Claims (5)

1. The use in a wallpaper ground coat of a copolymer emulsion latex having a solids contents of about 20% to about 70% by weight, preferably from about 40% to about 60%, wherein vinyl C1 to C13 alkanoate forms at least about 40% by weight of the monomer charge characterised in that
i) the polymerisation is performed in the presence of an effective amount of a stabilising surfactant having a C14 to C20 alkylene moiety, and
ii) the polymerised emulsion is reacted with an effective amount of an epoxy silane material.
2. A copolymer emulsion latex according to claim 1 wherein the comonomer is a C2 to C4 ethylenic hydrocarbon.
3. A copolymer emulsion latex according to any preceding claim wherein the stabilising surfactant is present in an amount of from about 1% to about 10% by weight, preferably 2% to 8%, relative to the copolymerisable monomers.
4. A copolymer emulsion latex according to any preceding claim wherein the epoxy silane is present at a level of about 0.1% to 3% by weight of emulsion.
5. A copolymer emulsion latex according to any preceding claim wherein the epoxysilane is present in an amount of from about 0.1% to about 3% by weight (dry) relative to the latex.
EP89312937A 1988-12-14 1989-12-12 Preparation of a wallpaper pigmented ground coat Expired - Lifetime EP0375244B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89312937T ATE102669T1 (en) 1988-12-14 1989-12-12 MAKING A PIGMENTED PRIMER ON A WALLPAPER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888829148A GB8829148D0 (en) 1988-12-14 1988-12-14 Emulsion polymerisation
GB8829148 1988-12-14

Publications (3)

Publication Number Publication Date
EP0375244A2 true EP0375244A2 (en) 1990-06-27
EP0375244A3 EP0375244A3 (en) 1990-08-08
EP0375244B1 EP0375244B1 (en) 1994-03-09

Family

ID=10648457

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89312937A Expired - Lifetime EP0375244B1 (en) 1988-12-14 1989-12-12 Preparation of a wallpaper pigmented ground coat

Country Status (7)

Country Link
EP (1) EP0375244B1 (en)
AT (1) ATE102669T1 (en)
AU (1) AU637588B2 (en)
CA (1) CA2005021A1 (en)
DE (1) DE68913687T2 (en)
FI (1) FI895917A7 (en)
GB (1) GB8829148D0 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG80567A1 (en) * 1996-02-26 2001-05-22 Rohm & Haas Latex compositions having improved drying speed
EP1914087A1 (en) * 2006-06-09 2008-04-23 Celanese International Corporation Synthetic nonwoven wallcoverings with aqueous ground coating

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8829147D0 (en) * 1988-12-14 1989-01-25 Unilever Plc Emulsion polymers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998991A (en) * 1974-03-29 1976-12-21 General Motors Corporation Transparent abrasion-resistant coating for a styrene acrylonitrile copolymer and method
GB8710912D0 (en) * 1987-05-08 1987-06-10 Unilever Plc Emulsion copolymerisation
GB8829147D0 (en) * 1988-12-14 1989-01-25 Unilever Plc Emulsion polymers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG80567A1 (en) * 1996-02-26 2001-05-22 Rohm & Haas Latex compositions having improved drying speed
EP1914087A1 (en) * 2006-06-09 2008-04-23 Celanese International Corporation Synthetic nonwoven wallcoverings with aqueous ground coating

Also Published As

Publication number Publication date
DE68913687T2 (en) 1994-10-13
EP0375244B1 (en) 1994-03-09
FI895917A7 (en) 1990-06-15
ATE102669T1 (en) 1994-03-15
FI895917A0 (en) 1989-12-12
AU637588B2 (en) 1993-06-03
EP0375244A3 (en) 1990-08-08
CA2005021A1 (en) 1990-06-14
DE68913687D1 (en) 1994-04-14
GB8829148D0 (en) 1989-01-25
AU4618089A (en) 1990-06-21

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