GB2103115A - Coating a paper web - Google Patents

Coating a paper web Download PDF

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Publication number
GB2103115A
GB2103115A GB08219643A GB8219643A GB2103115A GB 2103115 A GB2103115 A GB 2103115A GB 08219643 A GB08219643 A GB 08219643A GB 8219643 A GB8219643 A GB 8219643A GB 2103115 A GB2103115 A GB 2103115A
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GB
United Kingdom
Prior art keywords
roll
web
coating
nip
liquid solution
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
GB08219643A
Other versions
GB2103115B (en
Inventor
Robert Jacob Alheid
Robert William Carlson
Gerald Richard Garde
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beloit Corp
Original Assignee
Beloit Corp
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 Beloit Corp filed Critical Beloit Corp
Publication of GB2103115A publication Critical patent/GB2103115A/en
Application granted granted Critical
Publication of GB2103115B publication Critical patent/GB2103115B/en
Expired legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22Addition to the formed paper
    • D21H23/52Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56Rolls
    • D21H23/58Details thereof, e.g. surface characteristics, peripheral speed
    • D21H23/60Details thereof, e.g. surface characteristics, peripheral speed the material on the applicator roll being subjected to a particular treatment before applying to the paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22Addition to the formed paper
    • D21H23/52Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56Rolls
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H5/00Special paper or cardboard not otherwise provided for
    • D21H5/0005Processes or apparatus specially adapted for applying liquids or other fluent materials to finished paper or board, e.g. impregnating, coating
    • D21H5/0025Processes or apparatus specially adapted for applying liquids or other fluent materials to finished paper or board, e.g. impregnating, coating by contact with a device carrying the treating material
    • D21H5/003Processes or apparatus specially adapted for applying liquids or other fluent materials to finished paper or board, e.g. impregnating, coating by contact with a device carrying the treating material with a roller
    • D21H5/0032Details thereof, e.g. surface characteristics, peripheral speed
    • D21H5/0035Details thereof, e.g. surface characteristics, peripheral speed the coating material on the applicator roller being subjected to a particular treatment before applying to paper

Landscapes

  • Coating Apparatus (AREA)
  • Paper (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Paper webs travelling at up to 5000 ft/min are coated with starch solution by passage through nip 33 of press rolls 31, 32. Starch is applied in excess to the rolls by rolls 45 or a fountain (Fig. 4), and metered by blades 38, 39. <IMAGE>

Description

SPECIFICATION Apparatus and method for applying a coating to a paper sheet web The invention relates to coating treatment for a continuous paper web and, more particularly, to a system for such treatment which avoids the formation of large coating ponds and is capable of handling coating having a low solids and viscosity content at high running speeds.
In paper manufacture, it is well known to apply starch solutions to a continuous paper web in order to provide adequate body strength for the resulting paper sheets. During this process, the paper is coated with the starch on both sides for a proper penetration into the web.
Starch treatment assemblies have conventionally called for maintenance of a starch pond or puddle in a nip between two rolls before application to the web. One conventional device is a two roll press wherein the web is passed between two smooth rolls supporting a starch pond in a receiving nip between the rolls. The web passes generally centrally through the pond such that both sides of the web are simultaneously penetrated by the starch. The problem which arises in this technique is that, during high speed paper flow in excess of 2000 feet per minute (610 metres per minute), turbulence is generated in the starch puddle which tends to throw coating away from the nip and result in uneven application.
There are no means in the two roll press to control turbulence in the starch pond and uneven coating can result in breaking of the sheet web.
Another system using a starch pond is a gate roll press which has a series of contiguous smooth rolls in relative rotation. Two relatively large centre applicator rolls define a nip through which a continuous sheet web passes. Leading to each large applicator roll is a pair of relatively smaller metering or gate rolls which define a nip away from the applicator roll supporting a starch pond.
From the pond, starch film is carried along the rolls and applied to both sides of the web as it passes through the nip between the large rolls. A gate roll press will allow operating speeds up to 4,000 feet per minute (1220 metres per minute); however, it typically requires starch having higher viscosity levels to provide starch film strength through the gate roll nips. Due to the higher solids content required for viscosity, starch penetration in a gate roll press is minimal Optimum starch penetration requires low-solids and low-viscosity solutions.
High solids starches lead to high concentrations of starch on the outer surfaces of the web which may produce undesired web qualities such as sheet tackiness and bonding. Further, since starch penetration is limited, the internal bond strength of sheets treated in a gate roll press is generally not improved as are sheets treated in a two roll press.
The present invention is directed to a film applicator system which eliminates the need for starch pond formation and is able to apply penetrant starch treatment of webs at high speeds.
According to the invention there is provided apparatus for applying a coating to a paper sheet web in the form of a liquid solution for penetration into the web comprising: a two roll press defined by two rolls receiving the web therebetween, a nip between said rolls where the web enters for passage through said two roll press, coating applicator means for at least one roll for applying liquid solution onto said respective roll surface, and a doctor blade means cooperating with said at least one roll for metering the liquid solution on the respective roll surface into a generally uniform film to be passed to said nip for penetration into said web, whereby puddle formation is eliminated at said nip.
The invention also provides a method for high speed coating of a continuous paper web, comprising: passing said web at speeds over 1000 feet per minute (305 metres per minute) through a nip between two rolls, supplying coating onto the surface of at least one of said rolls, metering said coating on said respective roll surface into a generally uniform film slightly less than the maximum amount said web can absorb at said nip, and conducting said film and said respective roll surface into contact with said web at said nip.
The following is a detailed description of embodiments of the invention, reference being made to the accompanying drawings in which: Figure 1 is a schematic side elevational view illustrating a known two roll press arrangement wherein a paper web is passed through a starch pond, Figure 2 is a schematic side elevational view of a known gate roll press arrangement in which a starch pond held by gate rolls passes as film onto two press rolls for application on the surface of a paper web passing between the press rolls, Figure 3 is a schematic side elevational view of a film applicator system according to the present invention, where applicator roll means are used to deposit starch onto press rolls for metering, Figure 4 is a diagrammatic side elevational view of another embodiment of a film applicator system according to the present invention, using fountain means for depositing starch onto the press rolls for metering, Figure 5 is a fragmentary, schematic side elevational view illustrating the blade tip surface alignment with a respective press roll for use with the embodiment of Figures 3 and 4, Figure 6 is a fragmentary, schematic side elevational view of another embodiment of a film applicator system according to the present invention where an elastically deformable blade is used for metering, and Figure 7 is a fragmentary, schematic side elevational view illustrating desirable blade tip alignment with a respective press roll for use with the embodiment of Figure 6.
The invention is here described for use in the starch treatment of paper web; however, the inventive apparatus will have application generally to coating to paper sheets or sheet web.
Figure 1 illustrates a two roll size press arrangement 10 for treating a continuous paper web 11 with starch from a large starch pond 1 2 in a manner known in the art. The pond 12 is supported in the nip between two rolls 1 3 and 14 through which the web is passed. This arrangement has been found to have limitations at web speeds in excess of about 2000 feet per minute (610 metres per minute) due to the creation of pond turbulence. The turbulence tends to throw starch coating away from the nip and can result in breaking of the sheet web. Turbulence is reduced by using lower starch viscosities, but higher water evaporation is then required in the web drying process.Additionally, amounts of lower viscosity starch onto a web cannot be effectively controlled by nip pressure and the amounts of coating on a web tend to increase with machine speed. Therefore, the approach to controlling the amount of starch coating on a web in a two roll size press has been to use a low solids content (4-6 percent) starch pond solution.
In Figure 2, a conventional gate roll press system 20 for starch treatment is shown. The paper web 11 passes between two press rolls 21 and 22, each of which has been coated with starch by means of a gate roll arrangement. Both gate roll arrangements are identical such that only one need be described. Two adjacent gate or metering rolls 23 and 24 support a starch pond 25 in their nip. The metering rolls and press rolls are in contiguous series relation for the passage of starch therebetween and rotate relative to one another. In order to apply a starch coating to the intermediate gate roll 23 for passage onto the press roll 22, the outer gate roll 24 rotates at approximately 40 percent of sheet web speed, while the middle roll 23 rotates at approximately 60 percent sheet speed.The starch film formed on the press roll 22 passes to a nip 26 formed between the press rolls, where starch deposits on one surface of the paper web. The gate roll press arrangement enables starch treatment at paper web speeds up to 4,000 feet per minute (1220 metres per minute); however, surface coating only results due to the high viscosity starch solutions commonly used in gate roll presses. It is difficult to support the starch pond in the gate rolls when the viscosity becomes too low; so conventional gate roll press starch solutions have generally not had less than 10 percent solids content. Insufficient starch penetration causes the thus produced sheets to be of lower internal bond strength than sheets produced with a two roll size press.
In accordance with the present invention, a two roll press is provided in which a continuous paper web 11 (Figures 3 and 4) passes between two smooth applicator or press rolls 31 and 32 which form a nip 33 at the point of entry of the web therebetween. Adjacent to each roll is a respective doctor blade assembly 34 and 35 having blade holder housings 36 and 37 for adjustably containing blade elements 38 and 39 extending obliquely toward the outer surfaces of the rolls.
The doctor blade assemblies 34 and 35 utilise straight, bevelled blades 38, 39 (Figure 5) which are pivotably adjustable to necessary angles relative to the applicator rolls to meter a film thickness F over the rolls downstream of the blades 38 and 39. The blades 38 and 39 may be of metal such as steel. However, the blades should be made of a material, such as Teflon, which is softer than the corresponding applicator rolls 31 and 32, which are preferably made of, or covered by, hard rubber (0--50 P and J). The relatively softer blades minimise wear on the rolls. Although the blades will wear more quickly, their replacement is simple and easy.
The straight blades 38 and 39 (Figures 3 and 4) are preferably adjusted by flexible bladder means 40 and 41 which expand and contract under air pressure for selective positioning of the doctor blades. Such air tube loaded doctor blades are generally known in the art. Some typical examples are set forth in U.S. Patent Specifications Nos.
3,529,315 and 3,778,861.
Each press roll 31 and 32 is coated with a starch solution from a corresponding starch applicator means 42 and 43 upstream of the film metering blades. The starch deposited on each press roll is approximately 10 to 40 times the volume of starch film being passed to the web entry nip 33 by the metered film. A build-up or pool of solution accordingly develops upstream of the blade tips. Preferably, the treatment film thickness F on each applicator roll is set so as to be slightly less than the maximum amount that can be absorbed by that respective side of the web 11. Thus, there is substantially no starch puddle formation at the nip 33. Since no starch pond is required in the inventive arrangement, the web 11 may pass upwardly or downwardly between the rolls 31 and 32.
In Figure 3, the starch applicator means is in the form of an applicator roll arrangement, wherein applicator rolls 44 and 45 extend between the corresponding large press rolls 31 and 32 and a supply of starch solution S contained in respective basins 46 and 47. The applicator rolls serve to coat the outer surfaces of the large rolls 31 and 32 with the supply of starch.
Alternatively, as illustrated in Figure 4, a supply of starch is deposited on the respective large press rolls 31 and 32 by means of fountains which deliver liquid solution under pressure through delivery nozzle means 48 and 49. Starch solution is pumped into a respective fountain delivery line through conduit means by a pump P, such as a variable speed positive displacement pump. The pump delivers starch solution from reservoirs or tanks 51 and 52, respectively, which hold a solution supply.
Alternatively to the straight blade arrangements shown in the embodiments of Figures 3 to 5, the inventive film applicator system may utilise an elastically deformable doctor blade device 50, as shown in Figure 6, to meter the film F to the nip 33. Such a deformable metering blade system is described in British Patent Specification No.
1,424,1 50. For purposes of illustration, an applicator roll 45 mechanism as discussed above serves to coat the respective press roll 32, although a fountain means could be used instead.
The film metering criterion remains the same as above.
The elastically deformable blade device 50 is disposed downstream of the applicator roll 45.
This device comprises a blade holder frame 51 for supporting a deformable, steel doctor blade 52.
One end of the blade 52 is fixably embedded in a lower end 53 of the frame. The other end of the blade extends freely outward of the frame. The frame 51 is pivotable about a pivot shaft 54 by suitable operating means, such as indicated by an hydraulic cylinder 55 which extends a link pin 56 connected to the lower end of the frame 53.
The blade 52 is initially disposed in an undeformed, straight-line fashion as shown in the rightmost chain line position of the frame 51 in Figure 6. Outward extension of the link 56 pivots the holder frame 51 into working positions. The blade's free end rests at the point P and the blade 52 is concavely arced or bent by the intermediate engagement therealong with a platform vertex 58.
It is desirable to set the blade 52 and holder frame pivot shaft 54 so that the blade tip surface 57 faces the press roll 32 substantially tangentially at point P as shown in Figure 7. Such positioning ensures that the meteredf(lm is uniform and accurate despite changes in the blade bending load as indicated by the blade movements between the chain and solid line positions in Figure 6.
Smoothness and uniformity of the film F is maintained by keeping the flat blade tip surface 57 in tangential engagement with the press roll 32. The thickness of the film F is controlled by adjustment of the blade load or degree of blade deformation produced by the pivotal rotation of the holder frame 51.
Proper starch penetration is necessary to improve internal sheet strength. A major factor in controlling starch penetration is the solids level and viscosity of the starch. Both low solids and low viscosity are required to get optimum starch penetration into a web. In the conventional puddle arrangements, the starches typically have low solids contents (i.e., about 6%) with high viscosity.
The precise metering of the present invention system enables low solids (less than 10% and preferably about 5%) -- low viscosity starches to be used in the treatment of a sheet web running at speeds ranging from approximately 1000 to 5000 feet per minute (305 to 1 525 metres per minute).
The above disclosed embodiments depict systems which preferably treat both sides of a web simultaneously but staggered surface treatments are also within the scope of the present invention.

Claims (19)

1. Apparatus for applying a coating to a paper sheet web in the form of a liquid solution for penetration into the web comprising: a two roll press defined by two rolls receiving the web therebetween, a nip between said rolls where the web enters for passage through said two roll press, coating applicator means for at least one roll for applying liquid solution onto said respective roll surface, and a doctor blade means cooperating with said at least one roll for metering the liquid solution on the respective roll surface into a generally uniform.film to be passed to said nip for penetration into said web, whereby puddle formation is eliminated at said nip.
2. Apparatus according to claim 1, wherein said coating applicator means comprises an elastic member for metering the liquid solution onto at least one roll of said two roll press, said two roll press transporting said web at speeds between 1000 and 5000 feet per minute (305 to 1525 metres per minute).
3. Apparatus according to claim 1 or claim 2, wherein the coating applicator means include a portion to apply to said roll surface 10 to 40 times the volume of the liquid solution film being passed to said nip by said respective roll.
4. Apparatus according to any of claims 1 to 3, wherein said coating applicator means comprise a respective fountion for said respective roll, said fountain having a delivery line and a pump for passing a flow of liquid solution under pressure through said delivery line.
5. Apparatus according to any of claims 1 to 3, wherein said coating applicator means comprise an applicator roll arrangement for said respective roll, said applicator roll arrangement comprising an applicator roll between its respective roll and a basin of liquid solution whereby said applicator roll picks up solution from said basin and deposits it onto the surface of said respective roll.
6. Apparatus according to any of claims 1 to 5, wherein said doctor blade means comprise adjustable blade mounting means and a straight blade made of material softer than the outer surface material of said respective roll.
7. Apparatus according to claim 6, wherein said blade mounting means include air pressure tube means for relative adjustment of the pressure between said blade and said respective roll surface.
8. Apparatus according to any of claims 1 to 7, wherein said doctor blade means comprise an elastically deformable blade, one end of which abuts against said respective roll surface and the other end of which is fixed in a blade holder frame, means for pivoting said frame about an axis, and a surface portion on said frame for concavely bending said blade according to the amount of pivotal movement of said frame to adjust thickness for said liquid solution film.
9. Apparatus according to claim 8, wherein said blade has a flat tip surface that is always substantially tangential with said respective roll surface for metering said liquid solution film.
10. Apparatus according to claim 6, wherein said straight blade has a bevelled tip surface which is always substantially tangential with said respective roll surface for metering said liquid solution film.
11. Apparatus according to any of claims 1 to 10, wherein the liquid solution is a starch solution having a solids content of less than 10%.
12. Apparatus according to any of claims 1 to 11, further comprising means for passing said web through said two press rolls at speeds between 1000 and 5000 feet per minute (305 to 1525 metres per minute).
13. Apparatus according to any of claims 1 to 12, further comprising another coating applicator means and another doctor blade means associated with the other roll, whereby liquid solution film contacts said web on both sides at said nip.
14. Apparatus according to any of claims 1 to 13, wherein said doctor blade means meter said liquid solution film to slightly less than the maximum amount said web can absorb at said nip.
1 5. Apparatus according to any of claims 1 to 1 5, further comprising means for passing said web through said two roll press at speeds over 3,000 feet per minute (913 metres per minute).
1 6. A method for high speed coating of a continuous paper web, comprising: passing said web at speeds over 1000 feet per minute (305 metres per minute) through a nip between two rolls, supplying coating onto the surface of at least one of said rolls, metering said coating on said respective roll surface into a generally uniform film slightly less than the maximum amount said web can absorb at said nip, and conducting said film and said respective roll surface into contact with said web at said nip.
1 7. A method according to claim 16, further comprising: supplying said coating on said respective roll surface at 10 to 40 times the volume of said coating transmitted to said nip.
1 8. Apparatus for applying a coating to a paper sheet web substantially as hereinbefore described with reference to any of Figures 3 to 7 of the accompanying drawings.
19. A method of applying a coating to a paper sheet web according to claim 1 6 and substantially as hereinbefore described with reference to the accompanying drawings.
GB08219643A 1981-08-06 1982-07-07 Coating a paper web Expired GB2103115B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US29047981A 1981-08-06 1981-08-06

Publications (2)

Publication Number Publication Date
GB2103115A true GB2103115A (en) 1983-02-16
GB2103115B GB2103115B (en) 1984-12-12

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Family Applications (1)

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GB08219643A Expired GB2103115B (en) 1981-08-06 1982-07-07 Coating a paper web

Country Status (9)

Country Link
JP (1) JPS5830365A (en)
KR (1) KR860001633B1 (en)
CA (1) CA1196181A (en)
ES (1) ES8307538A1 (en)
GB (1) GB2103115B (en)
IN (1) IN159200B (en)
IT (1) IT1152329B (en)
MX (1) MX158731A (en)
PH (2) PH23200A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60251959A (en) * 1984-05-11 1985-12-12 ジエー、エム、フオイト、ゲゼルシヤフト、ミツト ベシユレンクテル、ハフツング Apparatus for applying liquid onto advance web
US5159893A (en) * 1989-10-09 1992-11-03 Valmet Paper Machinery Inc. Method and apparatus for regulation of the moisture profile of a paper or board web in a film size press
DE4340039A1 (en) * 1993-11-24 1994-04-07 Voith Gmbh J M Web coating appts. - has applicator belts passing in a closed loop through press gap between rollers with the web and structured blanket deflection rollers for high speed
WO1995008026A1 (en) * 1993-09-14 1995-03-23 J. M. Voith Gmbh Process and device for coating a travelling material web
CN103243610A (en) * 2013-04-12 2013-08-14 杭州维美机械有限公司 Paper web gluing process based on membrane transfer
EP2706143B1 (en) 2011-12-02 2016-09-28 Mudanjiang Hengfeng Paper Co., Ltd Manufacturing device and preparation method for cigarette paper having flame-retarding stripes
CN115025940A (en) * 2022-06-10 2022-09-09 北京工商大学 3D prints modified equipment on stainless steel profiled surface
EP3830336B1 (en) 2018-07-27 2023-02-22 Voith Patent GmbH Method and device for starch application

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60215764A (en) * 1984-04-09 1985-10-29 Nippon Steel Corp Formation of film
DE3440634C2 (en) * 1984-11-07 1986-09-11 J.M. Voith Gmbh, 7920 Heidenheim Device for double-sided coating of moving webs
US7669547B2 (en) 2001-03-14 2010-03-02 3M Innovative Properties Company Coating apparatus

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60251959A (en) * 1984-05-11 1985-12-12 ジエー、エム、フオイト、ゲゼルシヤフト、ミツト ベシユレンクテル、ハフツング Apparatus for applying liquid onto advance web
US4848268A (en) * 1984-05-11 1989-07-18 J. M. Voith Gmbh Apparatus and method for applying a liquid to a moving web
US5159893A (en) * 1989-10-09 1992-11-03 Valmet Paper Machinery Inc. Method and apparatus for regulation of the moisture profile of a paper or board web in a film size press
US5304391A (en) * 1989-10-09 1994-04-19 Valmet Paper Machinery Inc. Method for regulation of the moisture profile of a paper or board web in a film size press
WO1995008026A1 (en) * 1993-09-14 1995-03-23 J. M. Voith Gmbh Process and device for coating a travelling material web
US6203858B1 (en) 1993-09-14 2001-03-20 Voith Sulzer Papiermaschinen Gmbh Method and system for coating a web
DE4340039A1 (en) * 1993-11-24 1994-04-07 Voith Gmbh J M Web coating appts. - has applicator belts passing in a closed loop through press gap between rollers with the web and structured blanket deflection rollers for high speed
US5578125A (en) * 1993-11-24 1996-11-26 Voith Sulzer Papiermaschinen Gmbh Coating system for running webs of paper or cardboard
EP2706143B1 (en) 2011-12-02 2016-09-28 Mudanjiang Hengfeng Paper Co., Ltd Manufacturing device and preparation method for cigarette paper having flame-retarding stripes
CN103243610A (en) * 2013-04-12 2013-08-14 杭州维美机械有限公司 Paper web gluing process based on membrane transfer
EP3830336B1 (en) 2018-07-27 2023-02-22 Voith Patent GmbH Method and device for starch application
CN115025940A (en) * 2022-06-10 2022-09-09 北京工商大学 3D prints modified equipment on stainless steel profiled surface

Also Published As

Publication number Publication date
GB2103115B (en) 1984-12-12
IT8222744A0 (en) 1982-08-05
MX158731A (en) 1989-03-08
ES514269A0 (en) 1983-08-01
ES8307538A1 (en) 1983-08-01
CA1196181A (en) 1985-11-05
IN159200B (en) 1987-04-11
PH23768A (en) 1989-11-03
KR860001633B1 (en) 1986-10-14
KR840001291A (en) 1984-04-30
PH23200A (en) 1989-06-06
JPS5830365A (en) 1983-02-22
IT1152329B (en) 1986-12-31

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PE20 Patent expired after termination of 20 years

Effective date: 20020706