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WO1993018228A1 - Procede pour traiter et appreter des substrats de papier - Google Patents

Procede pour traiter et appreter des substrats de papier

Info

Publication number
WO1993018228A1
WO1993018228A1 PCT/EP1993/000229 EP9300229W WO9318228A1 WO 1993018228 A1 WO1993018228 A1 WO 1993018228A1 EP 9300229 W EP9300229 W EP 9300229W WO 9318228 A1 WO9318228 A1 WO 9318228A1
Authority
WO
WIPO (PCT)
Prior art keywords
isocyanate
paper
range
electrode
paper substrate
Prior art date
Application number
PCT/EP1993/000229
Other languages
English (en)
Inventor
Paul David Coleman
John Russell Robertson
Original Assignee
Imperial Chemical Industries Plc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to JP51527593A priority Critical patent/JP3176627B2/ja
Priority to AU48079/93A priority patent/AU668758B2/en
Priority to DE69301029T priority patent/DE69301029T2/de
Priority to EP93905232A priority patent/EP0628108B1/fr
Publication of WO1993018228A1 publication Critical patent/WO1993018228A1/fr

Links

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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention is concerned with a pro ⁇ cess for treating and sizing paper substrates with an isocyanate.
  • the present invention is concerned with a process for strengthening and sizing paper with an isocyanate characterized in that the isocyanate does not contain water and is applied to paper by means of an electrostatic spray ⁇ ing device.
  • Isocyanates emulsified with water have been applied to paper using a size press and unemulsified isocyanates have been applied using a rotogravure coating machine.
  • conventional means of spray ⁇ ing isocyanates are used, they are characterized by low transfer efficiencies. As a result, significant amounts of isocyanate are released into the atmo ⁇ sphere, thereby creating potential health problems.
  • the isocyanate that is applied to paper is not sprayed, solvent diluted, or emulsi ⁇ fied, it is very difficult to apply the isocyanate at levels below 5 to 10 percent by weight based upon the weight of the paper. Lower isocyanate levels can be achieved by using emulsified isocyanates.
  • Electrostatic spraying devices as such are known. See, for example, United States Patent Nos. 4854506 and 4846407 and EPA-193348. The electro ⁇ static spraying of various polymeric materials onto paper has also been disclosed in United States Pat ⁇ ent Nos. 3930614, 4609686 and 4837057.
  • the process of this invention is a process for treating a paper substrate with an isocyanate com ⁇ prising the step of applying an isocyanate which does not contain water to the paper substrate by means of an electrostatic spraying device.
  • the process for treating a paper substrate w-ith an isocyanate com ⁇ prises the step of applying an isocyanate which does not contain water to the paper substrate by means of an electrostatic spraying device which is comprised of an electrostatic sprayhead having a linear ori ⁇ fice, means for applying a first electrical poten ⁇ tial to liquid isocyanate which emerges from the sprayhead, an electrode comprised of two mutually spaced, parallel arranged linear electrode elements, with one electrode element being mounted adjacent to one side of the sprayhead , s orifice and the other element being mounted adjacent to the other side of the sprayhead , s orifice, and means for applying a second electrical potential to the electrode such that an intense electrical field is developed be ⁇ tween the emerging liquid and the electrode, the intensity ofthe field being sufficient to cause atomization of the emerging liquid, the electrode comprising a core of conducting or semiconducting
  • -3- material contained in a tubular sheath character ⁇ ized in that the sheath has a wall and the volume resistivity of a section of the wall of said sheath which is 1 cm in length is within the range of 5 x 10 11 to 5 x 10 n ohm cms.
  • the process of this invention provides light weight, uniform coatings of isocyanates on paper substrates and improves some of the physical proper ⁇ ties of coated paper substrates, such as water re- sistance, wet strength and crush strength.
  • the process involves the electrostatic spraying of isocyanates onto paper substrates.
  • the electro ⁇ static spraying device employed to spray isocyanates onto paper substrates preferably comprises an elec ⁇ trostatic sprayhead having a linear orifice, means for applying a first electrical potential to liquid isocyanate which emerges from the sprayhead, an electrode comprised of two mutually spaced, parallel arranged linear electrode elements, with one elec ⁇ trode element being mounted adjacent to one side of the sprayhead's orifice and the other element being mounted adjacent to the other side of the sprayh ⁇ ead's orifice, and means for applying a second elec ⁇ trical potential to the electrode such that an in ⁇ tense electrical field is developed between the emerging liquid and the electrode, the intensity of the field being sufficient to cause atomization of the emerging liquid, the electrode comprising a core of conducting or semiconducting material contained in a tubular sheath, characterized in that the sheath has a wall and the volume resistivity of a section of the
  • the isocyanate is charged at 30 to 40 kV by the means for applying an electrical potential to the isocyanate.
  • the isocy ⁇ anate is positively charged.
  • the liquid isocy ⁇ anate breaks into droplets having diameters typically ranging from 40 to 150 microns in an electric field created between the charged liquid and the electrode comprised of the two linear electrode elements, which are usually charged be ⁇ tween 10 kV and 25 kV and at the same polarity as the liquid.
  • the voltage difference be ⁇ tween the liquid isocyanate and the electrode com ⁇ prised of the two linear electrode elements is be ⁇ tween 15 and 30 kV. This voltage difference is called "stress.”
  • the isocyanates that are employed should have a viscosity in the range of 1 to 750 mPa.s, preferably in the range of 1 to 300, and a volume resistivity in the range of 1 x 10 6 to l x 10 11 ohm cms, prefera ⁇ bly in the range of 5 x 10 6 to 5 x 10 9 , and most preferably in the range of 5 x 10 7 to 5 x 10 8 ohm cms.
  • the higher the viscosity of the isocyanate the more difficult it is to apply the isocyanate.
  • isocyanate having one or more isocyanate groups and a viscosity and a resistivity between the above indicated limits can be employed.
  • the isocya ⁇ nates which may be used include aliphatic, cycloali- phatic, araliphatic and aromatic isocyanates, espe ⁇ cially those that are liquid at room temperature.
  • Aromatic isocyanates, especially aromatic polyisocy- anates, are preferred.
  • Mixtures of isocyanates can be used and also isocyanates which have been modi-
  • aromatic isocyanates in ⁇ clude m- and p-phenylenediisocyanate, toluene-2,4- and 2,6-diisocyanates, diphenylmethane-4, 'diisocya ⁇ nate, diphenylmethane-2,4'-diisocyanate, chlorophen- ylene-2,4-diisocyanate, diphenylene-4,4'-diisocyan ⁇ ate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3- methyldiphenylmethane-4,4'-diisocyanate and di- phenyletherdiisocyanate and 2,4,6-triiso-cyanatotol- uene and 2,4,4'-triisocyanatodiphenylether.
  • mixtures of isocyanates for example a mixture of toluene diisocyanate isomers such as the commercially available mixtures of 2,4- and 2,6-iso- mers and also the mixture of di and higher isocyana ⁇ tes produced by phosgenation of aniline/formaldehyde condensates.
  • Such mixtures are well known in the art and include the crude phosgenation products containing mixtures of methylene bridged polyphe- nylpolyisocyanates including diisocyanate, trii ⁇ ocy- anate and higher polyisocyanates together with any phosgenation by-products.
  • compositions of the present invention •are those wherein the isocyanate is an aromatic diisocyanate or polyisocyanate of higher functional ⁇ ity in particular crude mixtures of methylene bridged polyphenylpolyisocyanates containing diiso ⁇ cyanate, triisocyanate and higher functionality polyisocyanates.
  • the methylene bridged polyphenyl ⁇ polyisocyanates are sometimes referred to as poly ⁇ meric methylene polyphenyldiisocyanate (MDI) .
  • MDI poly ⁇ meric methylene polyphenyldiisocyanate
  • Poly ⁇ phenylpolyisocyanates are well known in the art and usually have an isocyanate functionality ranging from 2.0 to 3.0. They are prepared by phosgenation of corresponding mixtures of polyamines obtained by condensation of aniline and formaldehyde.
  • -6- I ⁇ ocyanate-terminated prepolymers may also be employed and are prepared by reacting an excess of polyisocyanate with polyols, including aminated polyols or imines/enamines thereof, or polyamines.
  • Emulsifiable isocyanates may also be employed.
  • An emulsifiable isocyanate is an isocyanate/i ⁇ ocyan- ate prepolymer blend which is made by incorporating into an isocyanate a prepolymer formed by reacting onoalkyl ethers of polyalkylene glycols or polyes ⁇ ter polyether glycols with a polyisocyanate to form an i ⁇ ocyanate terminated urethane adduct.
  • Such blends are well known to be emulsifiable in water. Suitable emulsifiable isocyanates and their prepara ⁇ tion are described in United States Patent Nos. 3,996,154 and 4,505,778, which are incorporated herein by reference.
  • emulsifiable MDI is the most preferred.
  • the most preferred aromatic isocyanates are polymeric MDI, emulsifiable MDI, MDI variants, and mixtures thereof.
  • Suitable MDI variant ⁇ include compounds in which the MDI has been modified by the introduction of urethane, allophanate, urea, biuret, amide, carbodiimide, uretonimine and/or isocyanurate residues.
  • Suitable aliphatic polyisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, saturated analogues of the above men ⁇ tioned aromatic isocyanate ⁇ , mixture ⁇ thereof and the like.
  • the isocyanate to be used i ⁇ a solid at the temperature of spraying, which temperature generally is 10 to 30°C and preferably 20 to 25°C
  • the iso ⁇ cyanate may be heated in order to liquefy it and the heated isocyanate can be sprayed.
  • the isocyanate should generally not be heated to temper-
  • the isocyanate is liquid at the spraying tempera ⁇ ture.
  • the liquid isocyanate is placed into a vessel from which the isocyanate can be pumped into the sprayhead of the electrostatic sprayer.
  • a hose connects the vessel and the electrostatic spra ⁇ yer.
  • the vessel is usually equipped with or con ⁇ nected to a means for pumping the isocyanate to the sprayhead at variable flowrates.
  • the flowrate can vary from 0.5 to 150 g/minute/cm of nozzle width, and preferably is in the range of 1.5 to 75 g/min ⁇ ute/cm of nozzle width.
  • the selected flowrate will depend upon factors such as how much isocyanate is to be applied to the paper substrate and the speed at which the paper substrate is passing below the nozzle of the sprayer.
  • a wide variety of paper ⁇ ubstrates can be trea ⁇ ted according to the process of this invention.
  • the process can be used to strengthen and size paper, corrugated paper containers, paper labels and paper- board.
  • the process is e ⁇ pecially u ⁇ eful in strengt ⁇ hening and sizing corrugated paper containers, such as container ⁇ that are likely to come into contact with moisture.
  • the paper sub ⁇ trate when being sprayed, needs to be in contact with a conducting surface in order to prevent the paper sub ⁇ trate from building up a charge due to the deposition of charged isocyanate particles on the surface of the paper substrate. If a charge builds up on the surface of the paper sub ⁇ strate, the charge will repel charged isocyanate particle ⁇ thereby leading to reduced transfer effi- ciencie ⁇ and a non-uniform coating of isocyanate on the paper substrate. In practice the paper sub ⁇ strate is usually in contact with a metal roller over which the paper substrate passes. However,
  • the nozzle is wider than the width of the paper substrate being sprayed so as to insure that the entire surface of the substrate is coated with isocyanate.
  • the distance of the nozzle from the surface of the paper substrate should be in the range of 7 to 23 cm. If the nozzle is too close, there can be sparking between the nozzle and the conducting surface in contact with the paper sub ⁇ ⁇ trate. Al ⁇ o, a ⁇ triped spray pattern may be pro ⁇ pokerd on the sub ⁇ trate.
  • the distance is greater than 23 cm, the charged isocyan ⁇ ate particles tend to spread out and wander thereby lowering the transfer efficiency and making it dif ⁇ ficult to have a uniform coating on the paper sub ⁇ strate.
  • the paper substrate can be treated on one side or both sides. If treated on both side ⁇ , it i ⁇ preferred for the isocyanate coating of the first treated side to be cured before treating the second side.
  • the isocyanates can be applied to paper substrates without being emulsified, it is not nec ⁇ essary to expose the substrate to a heat treatment
  • -9- step in order to drive off water that is used to emulsify isocyanates.
  • a heat treatment step in the process of this invention because heating the paper substrate after the isocyanate is applied promotes curing and can have a beneficial effect upon some of the physi ⁇ cal properties of the coated paper substrate, such as crush strength.
  • the paper substrate is usually exposed to a tempera- ture in the range of 65 to 205°C for about 1 to 30 ⁇ econds.
  • the heat treatment of the paper substrate usually takes place in an oven through which the substrate is passed.
  • additives which are compatible with the isocyanate and do not contain water can be mixed with the isocyanate prior to applying the isocyanate to the paper substrate.
  • propylene carbonate can be added to the isocyanate to modify the visco ⁇ ity of the isocyan- ate.
  • too much propylene carbonate should not be added because the propylene carbonate tends to lower the resistivity of the isocyanate.
  • the physical properties of the substrates can be improved. For example, the water resistance, the wet strength, and the crush strength of the substrates can be in ⁇ creased by using the process of this invention.
  • the proces ⁇ also results in a uniform distribution of isocyanate on the paper substrates. Since charged particles are employed in the process and the parti ⁇ cles seek to ground themselves instead of floating around in the atmosphere, the process results in greatly reduced levels of isocyanate in the atmo ⁇ sphere compared to conventional methods of applying isocyanates to paper substrates.
  • the electrostatic spraying device used was a device according to United States Patent No. 4854- 506 having a linear orifice and the following char ⁇ acteristics: the device was equipped with a linear noz ⁇ zle spraying blade having a width of about 50 cm (20 inches) the device was equipped with two field adjusting electrodes, which were two semi-conducting rods and which were placed parallel to the linear nozzle orifice at both sides.
  • Rubinate XI-241 which i ⁇ polymeric MDI, i ⁇ available from ICI Americas Inc or Rubicon Inc, has a visco ⁇ ity of 200 mPa. ⁇ , ha ⁇ a volume re ⁇ istivity of 1 x 10 8 ohm cms and is liquid at room temperature, was placed into a pressure vessel which was connect ⁇ ed to the electro ⁇ tatic spraying device.
  • the liquid isocyanate was delivered to the device from the pressure vessel using air at about 80 pounds/inch 2 .
  • the air pressure was regulated by means of a pressure regulator so as to give a flow rate of 40 g/min or 0.8 g/minute/cm of nozzle width.- The pressure was about 12 pounds/inch 2 .
  • the physical properties of the treated paper were tested and are set forth in Table I below.
  • the treated paper had excellent water re ⁇ istance and wet strength compared to an untreated piece of paper and had improved crush strength as well.
  • Example 1 was repeated except that 10% by weight of propylene carbonate was added to the poly ⁇ isocyanate. The amount of this composition applied to the paper calculated on the weight of paper was 3.5% by weight. The physical properties of the paper were tested and the results are set forth in Table I below.
  • the electrostatic spraying device of claim 1 wa ⁇ used to treat paper on a conventional paper coating machine.
  • a Carrier Ross roll coater machine was equipped with the electrostatic ⁇ praying device of claim 1 so that the paper would be sprayed prior to entering an oven.
  • the nozzle was situated six inches directly above a metal roller so that the paper would be in contact with the metal roller at the point where the isocyanate was sprayed onto the paper.
  • a roll of 651b/3000ft 2 bag paper comprised of 20 percent recycled newspaper was placed on the Carrier Ross machine and fed underneath the nozzle
  • the isocyanate sprayed onto the paper was Rubi- nate XI-242, which is a wate_r emulsifiable MDI, is available from ICI Americas Inc. and Rubicon Inc. , has a viscosity of 250 mPa.s, and has a volume re ⁇ sistivity of 5 x 10 7 ohm cms.
  • the charge on the isocyanate was -37.1 kV and the charge on the field adjusting electrodes was -18.1 kV.
  • the flowrate of the isocyanate was 40 g/min or 0.8 g/minute/cm of nozzle width.
  • the paper After being treated with the isocyanate, the physical properties of the paper were tested.
  • the paper had improved crush strength and exhibited a dramatic increase in water resistance and wet strength compared to an untreated piece of paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Le procédé pour renforcer et apprêter du papier avec de l'isocyanate est caractérisé en ce que l'isocyanate ne contient pas d'eau et qu'il est appliqué au papier par un dispositif linéaire d'électrospray. Le procédé permet d'appliquer efficacement l'isocyanate sans eau sur du papier en un pourcentage faible et d'une manière sûre pour l'environnement.
PCT/EP1993/000229 1992-03-02 1993-02-01 Procede pour traiter et appreter des substrats de papier WO1993018228A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP51527593A JP3176627B2 (ja) 1992-03-02 1993-02-01 紙基体の処理及びサイジングの方法
AU48079/93A AU668758B2 (en) 1992-03-02 1993-02-01 Process for treating and sizing paper substrates
DE69301029T DE69301029T2 (de) 1992-03-02 1993-02-01 Verfahren zur behandlung und leimung von papiersubstraten
EP93905232A EP0628108B1 (fr) 1992-03-02 1993-02-01 Procede pour traiter et appreter des substrats de papier

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US84434692A 1992-03-02 1992-03-02
US07/844,346 1992-03-02

Publications (1)

Publication Number Publication Date
WO1993018228A1 true WO1993018228A1 (fr) 1993-09-16

Family

ID=25292466

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000229 WO1993018228A1 (fr) 1992-03-02 1993-02-01 Procede pour traiter et appreter des substrats de papier

Country Status (9)

Country Link
EP (1) EP0628108B1 (fr)
JP (1) JP3176627B2 (fr)
AU (1) AU668758B2 (fr)
CA (1) CA2130922A1 (fr)
DE (1) DE69301029T2 (fr)
DK (1) DK0628108T3 (fr)
ES (1) ES2080613T3 (fr)
HK (1) HK191196A (fr)
WO (1) WO1993018228A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5961783A (en) * 1997-06-06 1999-10-05 Vinings Industries, Inc. Process for enhancing the strength and sizing properties of cellulosic fiber using a self-emulsifiable isocyanate and a coupling agent
DE19820432A1 (de) * 1998-05-07 1999-11-11 Voith Sulzer Papiertech Patent Verfahren und Vorrichtung zum Aufbringen eines Auftragsmediums auf einen laufenden Untergrund
EP2098638A3 (fr) * 2008-03-03 2011-01-26 Kronotec AG Procédé de couchage d'un papier humide ou encollé en forme de couche

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4305447B2 (ja) * 2003-03-31 2009-07-29 王子製紙株式会社 積層体、記録材料及びそれらの製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1156723A (fr) * 1956-09-13 1958-05-20 Schickedanz Ver Papierwerk Procédé pour enduire de couches du papier, du carton, ou autres matériaux fibreuxde ce genre
EP0186983B1 (fr) * 1984-12-20 1989-03-22 Imperial Chemical Industries Plc Pulvérisateur électrostatique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1156723A (fr) * 1956-09-13 1958-05-20 Schickedanz Ver Papierwerk Procédé pour enduire de couches du papier, du carton, ou autres matériaux fibreuxde ce genre
EP0186983B1 (fr) * 1984-12-20 1989-03-22 Imperial Chemical Industries Plc Pulvérisateur électrostatique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 009, no. 160 (C-289)4 July 1985 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5961783A (en) * 1997-06-06 1999-10-05 Vinings Industries, Inc. Process for enhancing the strength and sizing properties of cellulosic fiber using a self-emulsifiable isocyanate and a coupling agent
DE19820432A1 (de) * 1998-05-07 1999-11-11 Voith Sulzer Papiertech Patent Verfahren und Vorrichtung zum Aufbringen eines Auftragsmediums auf einen laufenden Untergrund
US6248407B1 (en) 1998-05-07 2001-06-19 Voith Sulzer Papiertechnik Gmbh Method for applying a coating medium onto a moving surface
US6503325B1 (en) 1998-05-07 2003-01-07 Voith Sulzer Papiertechnik Patent Gmbh Device and method for applying a coating medium onto a moving surface
EP2098638A3 (fr) * 2008-03-03 2011-01-26 Kronotec AG Procédé de couchage d'un papier humide ou encollé en forme de couche

Also Published As

Publication number Publication date
DK0628108T3 (da) 1996-05-06
JPH07504462A (ja) 1995-05-18
EP0628108A1 (fr) 1994-12-14
EP0628108B1 (fr) 1995-12-13
HK191196A (en) 1996-10-25
AU4807993A (en) 1993-10-05
DE69301029D1 (de) 1996-01-25
DE69301029T2 (de) 1996-05-30
AU668758B2 (en) 1996-05-16
JP3176627B2 (ja) 2001-06-18
ES2080613T3 (es) 1996-02-01
CA2130922A1 (fr) 1993-09-16

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