CN1510214A - Method for producing coated paper or paper board - Google Patents
Method for producing coated paper or paper board Download PDFInfo
- Publication number
- CN1510214A CN1510214A CNA2003101156894A CN200310115689A CN1510214A CN 1510214 A CN1510214 A CN 1510214A CN A2003101156894 A CNA2003101156894 A CN A2003101156894A CN 200310115689 A CN200310115689 A CN 200310115689A CN 1510214 A CN1510214 A CN 1510214A
- Authority
- CN
- China
- Prior art keywords
- coating
- coating curtain
- deck
- paper
- layer
- 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.)
- Pending
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
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
-
- 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
- D21H23/46—Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
- D21H23/48—Curtain coaters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/007—Slide-hopper coaters, i.e. apparatus in which the liquid or other fluent material flows freely on an inclined surface before contacting the work
- B05C5/008—Slide-hopper curtain coaters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/06—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying two different liquids or other fluent materials, or the same liquid or other fluent material twice, to the same side of the work
Landscapes
- Paper (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention refers to a method of producing a coated paper or paperboard, but excluding photographic papers, comprising the steps of: (a) forming a free flowing curtain comprising at least one layer, whereby the composition forming at least one layer of the free flowing curtain has a high shear viscosity of at least 50 mPa.s, and (b) contacting the curtain with a continuous web substrate of basepaper and paperboard.
Description
Technical field
The present invention relates to a kind of method of producing coated paper or cardboard.In addition, the invention still further relates to and a kind ofly under the situation of high shear, will have the method that full-bodied coating composition is coated substrate.
Background technology
Usually will compare the colored coating composition with quite high solids content and viscosity with photosensitive solution or emulsion and for example utilize the blade coating formula with the high linear speed that is higher than 1000m/min when making printing paper, rod (bar) formula or pair roller type (film) coating process are coated with.Paper or the continuous coating pigmented finiss of paperboard surface that any or all these methods are normally moving.
Yet, above-mentioned employed each method substantially all existence can cause bum a series of problems of coating surface.Under the situation of using blade coating formula coating process, the particulate deposits below blade can cause producing striped on coating, and this will reduce the quality of coated paper or cardboard.In addition, can in substrate, produce the breakage that a very high stress also can cause substrate for obtaining desired coating weight in the high pressure that applies on the scraper, thereby reduce production efficiency.And because pigmented finiss has high abrasion, in order to keep the smooth of coating top layer, scraper must often be changed.Equally, the inhomogeneous distribution that also can influence coating of substrate surface on paper or cardboard substrate surface.Coating can cause at the skewness of paper or paperboard surface and occur spot or variegated on the surface, thereby causes inferior printing effect.
Rod (bar) formula coating process is subjected to the solids content of applied pigmented finiss pigment and the restriction of viscosity.The solids content of the pigmented finiss that the bar type coating process is suitable for and viscosity are usually less than the used pigmented finiss of blade coating formula coating process.Therefore, for the bar type coating process, the amount that can be used for the coating on paper or cardboard substrate surface is impossible arbitrarily change.When these parameters of solids content, viscosity and coating weight of coating are unbalanced, will undesirably reduce the surface quality of coated paper or cardboard.And for keeping the smooth of coating top layer, the rod that is colored the coating abrasion needs periodic replacement.
Roller coat formula (film) coating process is a kind of complicated especially method of pigmented finiss being coated on paper or the cardboard, this is because for reaching the coating weight of each service speed and each requirement, the process conditions scope of the surface characteristics that relates to substrate, substrate porosity, solids coatings and the dope viscosity that must detect is narrower.Unbalanced meeting between these variablees causes forming irregular film on the surface of coated paper and splits pattern, thereby causes inferior printing effect, perhaps can deviate from the little gob that is coated with when thin plate leaves the coating roll gap.If these are coated with gob and are deposited on thin sheet surface again, can cause inferior printing effect.And the maximum coating content that uses roller coat formula coating process can coat paper or paperboard surface in a process is usually less than the amount of using blade coating formula or bar type coating process to be coated with.This to coating weight be limited in high-speed coating the time be very tangible.
The common trait of above-mentioned all methods is that the surface of paper substrate material has irregular mound and paddy usually, and the amount that is coated with feed liquid of coated paper base-material is to depend on that it is coating mound or paddy.Therefore, the thickness of coating and associated performance of ink will change along with the surface of coated paper, thereby cause the inhomogeneous of printed image.Although these shortcomings are arranged, because these coating processes are both economical, particularly have very high linear velocity, so these coating processes are still occupied an leading position in paper industry.
The common trait of above-mentioned all coating processes is to have full-bodied coating composition can not be used to coat substrates under the situation of high shear and/or shear-thickening behavior, its reason is that this coating composition can cause unacceptable coating defects, as producing striped or do not reach required coating weight on coating.And this coating composition demonstrates relatively poor water-retaining property and lower curing solids content usually.Coating with relatively poor water-retaining property can not be coated with above-mentioned coating process under the situation that does not reduce solids coatings and/or adding water retention agent usually.For drying efficiency, need under near the high solids coatings situation of solidifying solids content, be coated with in addition.This just means that it is difficult especially being coated with by aforementioned coating process with the low coating that solidifies solids content and low water-retaining property.
On the other hand, a trend being arranged in paper industry is that employed engineering pigment (engineeredpigments) has narrow particle size distribution and shape such as high-aspect-ratio, needle-like or other irregular shape and the interior porosity that occurs of calcined clay for example usually.Below the engineering coating of referred so-called co-structuredization coating also be developed.Term " co-structuredization pigment " should be understood that this pigment is modified, for example, and with specific granule and other specific particle aggregation; For example calcium carbonate granule is agglomerated on the talc particle, so in conjunction with the particular characteristic that is considered to improve paper such as opacity, gloss and printing performance.And this coating helps to improve the mechanical performance of paper.
When the engineering pigment that surpasses 20 weight % was added in the coating composition, said composition had high viscosity usually under high shear and/or shear-thickening behavior.This is because pigment can't be clamp-oned into effective tight structure under the situation of high-rate of shear.When its solids content during near solidification point, similar clamp-oning effect volume number and also can occur in traditional formulation for coating material under high-rate of shear.This phenomenon cause with aforementioned coating technique with this kind coating composition be coated on become on paper or the cardboard difficulty in addition impossible.As a rule, when shear rate greater than 100,000s
-1And when viscosity is higher than 50mPas, fluid ability will become problem.It has been generally acknowledged that it is difficult that coating that viscosity surpasses 75mPas flows, it then is unusual difficulty that coating that viscosity surpasses 100mPas flows.
In addition, the coating with shear-thickening behavior may flow on aforementioned device hardly.The shear-thickening behavior is a kind of phenomenon that also increases with shear rate increase viscosity.Shear rate when the shear-thickening behavior begins and viscosity all can change on a large scale with shearing the degree that increases.This two aspect of shear-thickening behavior is important and this two aspect depends on the solids content of coating fully.Among the present invention, the shear-thickening formulation for coating material is defined in shear rate and surpasses 1000s
-1The time, the variation of shear rate surpasses the prescription of an order of magnitude (10 times) viscosity increase at least 20%.
For some coating, the shear-thickening behavior begin and degree is a kind of unexpected transition, and represent the violent form of shear-thickening (dilatant) behavior.Among the present invention, this behavior is called as shears the retardance behavior, and it is defined as a kind of coating, the behavior of the increase of shear rate its viscosity increase at least 100% during less than an order of magnitude, and this shear rate is measured with the parallel-plate viscosimetry.The shear rate that begins to shear the retardance behavior can change and depend on especially solids content and coating factor and its particle size distribution of coating on a large scale.
Curtain coating is a kind of new relatively coating technique.EP-A517223 and Japanese patent application JP-94-89437, JP-93-311931, JP-93-177816, JP-93-131718, JP-92-298683, JP-92-51933, JP-91-298229, JP-90-217327 and JP-8-310110 have disclosed and have utilized coating method at paper surface coated one deck that moves or more pigmented finiss layer.More particularly,
Prior art is:
(i) coating method be used for the pigmented finiss single coating at the bottom of the raw base paper on paper, to produce the individual layer colored film.
(ii) before using the painted top layer of scraper coating process coating individual layer, coat a pigmented finiss bottom at the bottom of the raw base paper with coating method on.Therefore, just can make the painted coated paper of multilayer by carrying out painted coating continuously.
At the bottom of (iii) coating method is used for a painted top layer coated raw base paper, coat the individual layer pigmented finiss in advance with scraper coating process or metering roll coating process at first at the bottom of this raw base paper.Therefore, just can make the painted coated paper of multilayer by carrying out painted coating continuously.
At the bottom of (iv) coating method is used for the specific colored film of two simple layers coated raw base paper, so that these single coating are applied in coating process continuously.Therefore, just can make the painted coated paper of multilayer by carrying out painted coating continuously.
The content that prior art as discussed above is disclosed is coated the individual layer pigmented finiss use of the coating method on mobile paper wood surface and can be produced with respect to the coated paper surface of using traditional coating process to have better quality.Yet the continuous coating of using the curtain coating technology to carry out the pigmented finiss individual layer is subjected to the restriction of the kinetic factor in the coating method.Especially for light paint, can only under coating speed is lower than the situation of the used speed of traditional coating process of present use, could use, this be because under high coating speed this coating curtain (curtain) the unstable relatively poor coating surface that consequently forms that becomes.Unfortunately, no matter use above-mentioned any coating process, owing to quantity and quantity such as driver element, the drying equipment etc. of required ancillary hardware and the reasons such as space of placing these machines of required coating position, the continuous coating of paper or cardboard being carried out the pigmented finiss individual layer in continuous coating position remains the preparation technology who needs to drop into a large amount of capital.
The contained additive of coating layer is designed to have given functional coated paper and cardboard is called as functional product, these performances are such as being isolation, printability, cohesiveness, antistick characteristic and optical property such as color, brightness, opacity, gloss etc., and their coating is called functional coat.Can bring the paint ingredient of these characteristics to be also referred to as functional additive.Functional product comprises the paper as types such as self-adhesive paper, stamp paper, wallpaper, anti-adhesive silicone paper, food wrapper, greaseproof paper, moistureproof paper and saturated zone lining papers.
Coating method is used for multilayer and is coated with simultaneously and is known and is documented in patent US3508947 and 3632374, in order to apply photosensitive composition on paper and plastic matrix (web).Yet photosensitive solution and emulsion have low viscosity and low solid content, and can only be coated with under low coating speed.
Except the photosensitive material coating was used, it was known carrying out multi-layer coated preparation field at pressure-sensitive carbon paper simultaneously by coating method.For example, U.S. Pat 4230743 has disclosed in one embodiment, and the bottom and the second layer are coated on the mobile base-material simultaneously, and wherein bottom comprises the microcapsules as main component, and the second layer comprises a kind of color developer as main component.Yet, it is reported that this paper and the continuous coated paper that obtains have same character.In addition, this coating composition viscosity in the time of 22 ℃ that contains coloured developer is 10-20cps.
JP-A-10-328613 discloses with coating method two coatings has been coated on the paper substrate material simultaneously to make ink jet paper.According to the instruction of this reference paper, the coating composition of use is the aqueous solution that contains the utmost point low solid content of 8 weight %.In addition, need add thickener for the non-newtonian feature that obtains coating solution.It is acceptable that the embodiment that puts down in writing among the JP-A-10-328613 has illustrated that the coating quality when having only on-line velocity to be no more than 400m/min is only.Low running speed in the coating process is not suitable for producing economically printing paper, particularly common printed paper.
Above-mentioned document does not all disclose and under the situation of high shear full-bodied coating composition is coated on suprabasil method with the curtain coating technology.Above-mentioned document also discloses the coating composition that will have a shear-thickening behavior with the curtain coating technology and coats suprabasil method.
Summary of the invention
The essential technique problem that the present invention solves provides a kind of method of producing coated paper and cardboard, and is a kind of in the method in that to have full-bodied coating composition under the situation of high shear applied on described paper or cardboard.
Do not comprise that by a kind of production the coated paper of sensitive paper or the method for cardboard have solved this technical problem, this method may further comprise the steps: (a) formation comprises that flowing freely of one deck is coated with curtain (a free flowing curtain) at least, wherein form composition that one deck at least flows freely coating curtain layer 500,000s
-1Shear rate under have the shear viscosity of 50mPas at least, this shear viscosity is measured with capillary shear viscosity mensuration hereinafter described, will be coated with act with the continuous body paper and the web substrate of cardboard with (b) to contact.
In yet another embodiment of the present invention, may further comprise the steps in order to the production coated paper that solve the technical problem or the method for cardboard: (a) form one comprise one deck at least flow freely the coating curtain, wherein form composition that one deck at least flows freely coating curtain layer and have at least 1.2 shear-thickening coefficient, will be coated with act with the continuous body paper and the web substrate of cardboard with (b) and contact at 25 ℃.
The shear-thickening coefficient is by 30,000s
-1Viscosity under the shear rate and 3,000s
-1Viscosity ratio under the shear rate determines.These viscosity numbers are recorded by the parallel-plate viscosimetry that describes in detail hereinafter.If 30,000s
-1The time viscosity greater than 3,000s
-1The time viscosity, the value of shear-thickening coefficient so at this moment will be greater than the value of the shear-thickening coefficient that shows the shear-thickening behavior.
Unexpectedly, when one deck at least comprises the composition with shear-thickening coefficient of at least 1.2, be possible with the coating in the substrate of coating curtain success in the step (a).Preferably, the shear-thickening coefficient is at least 1.3, preferredly is at least 1.4, most preferredly is at least 1.5.
In yet another embodiment of the present invention, may further comprise the steps in order to the production coated paper that solve the technical problem or the method for cardboard: (a) form one comprise one deck at least flow freely the coating curtain, wherein form the composition that one deck at least flows freely coating curtain layer and in the time of 25 ℃, show the retardance behavior of shearing, will be coated with act with the continuous body paper and the web substrate of cardboard with (b) and contact.
Viscosity value added when observing the shear rate value added less than 10 times is greater than 100% existence of confirming to shear the retardance behavior.This viscosity is recorded by the parallel-plate viscosimetry that is hereinafter described in detail.One preferred embodiment in, the flowing freely coating curtain in the step (a) is that a multilayer flows freely the coating curtain.According to the present invention, flow freely the coating curtain preferably by a curtain coating equipment coating of disposing the slip nozzle, described nozzle is in order to carry the multilayer liquid layer to form a continuous multi-layer coated curtain.Also alternatively, a kind of extrusion type feed head, such as clearance type mouth mould or have the nozzle of some adjacent extrusion nozzles can be used for putting into practice the present invention.
Preferably in the step (a) at least one deck flow freely coating curtain layer at 25 ℃ and 500,000s
-1Shear rate under have the shear viscosity of 75mPas at least, preferred 100mPas at least, most preferably 125mPas at least.
One preferred embodiment in, coated paper or cardboard are not pressure-sensitive carbon papers.The term that is used to herein " paper " also comprises cardboard, unless can not obviously conclude such explanation in using the context of this term.Term " does not comprise sensitive paper " and is interpreted as that all layers of the coating curtain that is used for the present invention's practice do not contain Ag-containing compound.Term " does not comprise pressure-sensitive carbon paper " and is interpreted as the combination that does not comprise microcapsule-type colour coupler and color developer in the individual layer of the coating curtain that is used for the present invention's practice or the different layers.
Multilayer of the present invention flows freely the coating curtain a bottom or boundary layer, a top layer and optional one or more internal layers.Instruction free-falling coating curtain according to the present invention can comprise other layer except that comprising the one deck at least with specific rheological behavior.Traditional formulation for coating material as colouring agent for paint in industry all can be used in the coating curtain.Each layer can comprise liquid, emulsion, suspension, dispersion liquid, solution or their combination.Coating of the present invention coating curtain comprises at least one deck, it is two-layer at least to it is desirable to, at least three layers, at least four layers, at least five layers or at least six layers or more multi-layered.Coating curtain layer can comprise one or more dope layers, one or more functional layer and/or one or more printed layers.
One deck at least among the present invention flows freely coating curtain layer and preferably includes at least a pigment.The example of the pigment that is suitable for comprises clay, kaolin, calcined clay, co-structuredization pigment, talcum, calcium carbonate, titanium dioxide, satin white, synthetic polymer pigment, zinc oxide, barium sulfate, gypsum, silica, synthetic magadiite (magadiite), gibbsite, mica and diatomite.These pigment can nature obtain, synthetic or processing.When these pigment are used in the coating composition, it shows the characteristic of the paper of improvement, as better opacity, and the glossiness of improvement and/or better printing performance.These pigment also can mixedly use.These pigment can have different shapes, comprise bulk known in the art, dendroid, tabular, needle-like, spherical, etc.An advantage of the present invention is that it having surprising ability aspect the pigment that uses Any shape, is included in unworkable acicular pigment in the blade coating formula method.
Beyond thought is can easily will be formulated in 500,000s with method of the present invention
-1Has engineering pigment application in the coating composition of 50mPas shear viscosity at least under the shear rate in substrate.
The shape of some pigment such as co-structuredization pigment and structure can be destroyed under high-rate of shear, thereby, the character of these pigment is caused adverse influence.Flow freely the composition of coating curtain layer as one deck at least, the shape of these pigment and structure are being lower than 500,000s
-1Destroyed under the shear rate, beyond thought is that method of the present invention can be coated the composition that comprises at least a this class pigment in the substrate.In the preferred implementation, the shear rate that the shape and the structure of described pigment caused adverse effect is less than 100,000s
-1, more preferably less than 50,000s
-1, most preferably at least 10,000s
-1
In another embodiment, the one deck at least in the step (a) flows freely coating curtain layer and comprises the pigment that at least a length-width ratio was at least 1.5: 1.Preferably, the length-width ratio of this pigment was at least 5: 1, preferred being at least 10: 1, even more preferably at least 15: 1, and most preferably at least 20: 1.Another preferred embodiment in, the length-width ratio of described pigment was at least 30: 1, preferred being at least 40: 1, and most preferably at least 60: 1.
Preferably, the one deck at least among the present invention flows freely coating curtain layer and comprises adhesive.This adhesive can be the known any adhesives of those skilled in the art.The example of these adhesives comprises: styrene-butadiene latex, styrene-acrylate latex, styrene-butadiene-acrylonitrile latex, styrene-acrylate-acrylonitrile latex, styrene-butadiene-acrylate-acrylonitrile latex, styrene-maleic anhydride latex, styrene-acrylate-maleic anhydride latex, polysaccharide, protein, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate and cellulose derivative.Multiple adhesive kind all can be from commercial acquisition.
Coating curtain of the present invention comprises one or more functional layers.The purpose of functional layer is to give coated paper required function.For example the selectable punction layer can provide printability, isolation constancy, antistick characteristic, cohesiveness and optical property such as the color, brightness, opacity, gloss etc. as moistureproof, anti-fragrance, waterproof and/or steam, anti-solvent, grease proofing, grease-proof and anti-oxidation characteristic, sheet stiffness, antiflex cracking, paper.The functional coating that viscosity is strong can not be coated with traditional continuous coating process usually, and this is to adhere to trend on deflector roll or other coating apparatus because the viscosity of coating has substrate.On the other hand, simultaneously multi-layer coating method this functional paint can be coated on top layer coating below, contact with coating machine to prevent this functional paint.
The solids content of functional layer can be very different according to desired function.In the functional layer gross weight, a functional layer of the present invention preferably has up to the solids content of 75 weight % with up to 3, the viscosity of 000cps (brookfield viscosity, rotating speed 5,100rpm, 25 ℃), more preferably 50-2,000cps.The coating weight of preferred function layer is 0.1-10g/m
2Be more preferably 0.5-3g/m
2In some cases, such as when using a dye coating, the coating weight of this functional layer can be less than 0.1g/m
2
Functional layer of the present invention can comprise the material of one or more, as: the ethylene, propylene acid polymer; Polyethylene; Other polyolefin; Polyurethanes; Epoxy resin; Polyester; Adhesive such as styrene butadiene latices; Styrene-acrylate latex; Carboxylate latex; Starch; Protein; Deng; Adhesive such as starch, styrene-propene acid copolymer, phenylethylene-maleic anhydride, polyvinyl alcohol, polyvinyl acetate, carboxymethyl cellulose etc.; Permeability-reducing admixture (barrier) is as ethylene-vinyl alcohol (ethylene vinyl alcohol), siloxanes, or wax etc.This functional layer can comprise, but is not limited to pigment or permeability-reducing admixture, is used for those of each coating as previously described.。
Among the present invention, be called as top layer at multi-layer coated curtain middle distance base paper layer farthest.One preferred embodiment in, the flowing freely coating curtain in the step (a) comprises a top layer that guarantees printability, this is because this one deck one deck normally to be printed.Coated paper of the present invention also can further be coated with in a conventional manner, as bar, scraper, roller, rod or airblade coating technology etc.This top layer can be dope layer or functional layer, comprises gloss layer.Of the present invention one preferred embodiment in, top layer is extremely thin, has for example 0.5-3g/m
2Coating weight.This advantageously allows below top layer and to use than cheap material, but still can produce the paper with good print performance.In one embodiment, top layer does not have coloring earth.
According to particularly preferred embodiment, top layer comprises a kind of polishing agent prescription.Polishing agent prescription and the new combination of multilayer curtain coating simultaneously combine the advantage of curtain coating and good gloss.
The prescription of the polishing agent that uses among the present invention comprises the gloss additive, as comprises the synthetic polymer pigment of hollow polymer pigment, and it is by polymerization such as styrene, third rare nitrile and/or acrylic monomers and obtain.The synthetic polymer pigment that is suitable for has 40-200 ℃ glass transition temperature, and more preferably 50-130 ℃, and the particle size of 0.02-10 μ m, more preferably 0.05-2 μ m.In solid, the polishing agent prescription comprises the gloss additive of 5-100 weight %, more preferably 60-100 weight %.Another kind of polishing agent prescription comprises gloss varnish, as based on epoxy acrylate, and polyester, polyester acrylate, polyurethanes, polyether acrylate, oleoresin, nitrocellulose, polyamide, those materials of the polyacrylate of ethylenic copolymer and various ways.
If the coating curtain haves three layers at least, it has one deck intermediate layer at least so.The viscosity in intermediate layer is not critical, as long as keep the stable of coating curtain.When existing more than one intermediate layer, functional layer and dope layer can combinedly use.For instance, these intermediate layers can comprise the combination of identical or different functional layer, the combination of identical or different dope layer, or the combination of dope layer and functional layer.
Boundary layer is and the contacted layer of substrate to be coated.A critical function of boundary layer is promote substrate wetting.Boundary layer can have more than one function.For example, except wetting, it can cover substrate, and improves such as tack, constancy, rigidity, or the performance that combines of these performances.In multi-layer coated curtain of the present invention, boundary layer is a coating that relatively approaches preferably.The suitable coating weight of boundary layer is 0.1-5g/m
2, preferred 1-3g/m
2In the weight of coating curtain median surface layer, the suitable solids content of boundary layer is 0.1-65%.In a specific embodiment, the solids content of boundary layer is relatively low, and preferred solids content is 0.1-40%.
In in a coating curtain gross weight, the scope of the solids content of coating curtain is 10-80 weight % in the step (a), preferred 20-75 weight %.In addition, the solids content that flows freely coating curtain in the preferred steps (a) is at least 30 weight %, preferred at least 40 weight %, more preferably at least 50 weight %, even more preferably at least 55 weight %, and at least 60 weight % most preferably.
According to one preferred embodiment, the solids content that forms one deck at least of compound free-falling coating curtain is higher than 60 weight % of this dope layer gross weight.In another one embodiment of the present invention, in the step (a) at least one deck flow freely coating curtain and have the solids content of at least 30 weight %, preferred at least 40 weight %, and at least 50 weight % most preferably.
Opposite with the technology of sensitive paper and pressure-sensitive carbon paper, method of the present invention can be utilized viscosity and highly filled coating curtain layer even the operating with high coating speed with wide region.
Method of the present invention can advantageously change the component and the relative thickness of each layer in multi-layer compound structure.The multilayer component can be according to by the grade of the paper produced and identical or different.For example, the thin layer that designs for tack near body paper, for an extremely thin top layer that provides thick internal layer that the sheet material bulk density designs and design for the printing of the best can be bonded in the multi-layer coated curtain, purpose is for a composite construction is provided.In another embodiment, one can be used for strengthening invisible and specially designed internal layer.Other embodiment of the layer of the changed coating weight in a layered composite comprises and is less than 2g/m
2Skim, this layer be as the top layer of composite coating, the one deck at least in internal layer or the bottom.Use method of the present invention, paper wood can be applied at one or both sides.
One preferred embodiment in, one deck at least in the step (a) flows freely coating curtain layer and suitably comprises the additive that those skilled in the art are known, as at least a surfactant, at least a dispersant, at least a lubricant, at least a water retention agent, at least a crosslinking agent, at least a fluorescent whitening agent, at least a pigment, dyestuff or colouring agent, at least a thickener, at least a defoamer, at least a antifoaming agent, at least a antimicrobial and/or soluble dye or colouring agent etc.Poly(ethylene oxide) is a kind of of preferred additives, can be applied to any layer.One preferred embodiment in, poly(ethylene oxide) is used as a kind of thickener, preferably uses at boundary layer at least.Advantageously, the weight average molecular weight of poly(ethylene oxide) is at least 50,000, and preferably at least 100,000, more preferably at least 500,000, most preferably at least 800,000.The consumption of preferred poly(ethylene oxide) will be enough to prevent cratering, preferably less than 2 weight %, in the weight of solid content used in this layer.
In another embodiment, the one deck at least in the step (a) flows freely the coating weight dry weight of coating curtain layer less than 10g/m
2, preferably less than 8g/m
2, most preferably less than 6g/m
2
In an embodiment of the invention, the continuous substrate in the step (b) had not both had the yet not pre-calendering of pre-coating.In another embodiment, web substrate is not by pre-coating film.In another embodiment, web substrate is not rolled in advance.Preferably, the continuous web substrate in the step (b) has the base-material speed of 300m/min at least, even more preferably 400m/min at least, most preferably 500m/min at least.In another embodiment, continuously web substrate has the speed of 800m/min at least, preferably 1000m/min at least.
Suitable every Gram Mass of described continuous web substrate, or basis weight is 20-350g/m
2
Description of drawings
Fig. 1 is a cross-sectional view, and it is expressed as carries the multiple flow 3 that is coated with the curtain layer to form continuous 4 curtain coating equipment 1 that preferably have a sliding nozzle device 2 of multi-layer coated curtain.When reaching a dynamic equilibrium, flow into the coating curtain laminar flow amount and the flow complete equipilibrium that flows out sliding nozzle device of sliding nozzle device 2.The multi-layer coated curtain of free-falling 4 contacts with the base-material 5 of continuous service, thereby base-material 5 is coated with by corresponding coating curtain layer multi-layer.Base-material 5 changes moving direction at once by a roller 6 and drops to minimum with the influence that the air that is accompanied by fast moving base-material 5 is flowed before dispensing area.
The specific embodiment
The present invention illustrates by following examples.Unless otherwise noted, all umbers and percentage are all taked weight basis.
Embodiment
Prescription
Be coated with and used following material in the feed liquid:
Carbonate (A): 90% particle size is less than 2 microns calcium carbonate water dispersion (HYDROCARB 90 ME come from Plauess-Srauffer), solids content 77%.
Carbonate (B): 60% particle size is less than 2 microns calcium carbonate water dispersion (HYDROCARB 60 ME come from Plauess-Srauffer), solids content 77%.
Carbonate (C): narrower and 75% the particle size of particle size distribution is less than 2 microns engineering calcium carbonate water dispersion, (CARVERCARB 75, come from Plauess-Srauffer), solids content 72%.
Carbonate (D): 36% particle size is Powdered less than 2 microns calcium carbonate (MILLINGCARB OG comes from Plauess-Srauffer).
Clay (A): the water dispersion of calcined clay (ANSILEX 93, the calcined kaolin particulate, and particle size distribution is that the particle size of 86-90% is less than 2 microns, average particle size particle size is 0.8 micron, solids content 50% comes from Engelhard Corporation, Iselin NJ).
Clay (B): the clay water dispersion of high-aspect-ratio (KSZ 81, come from AKW-Kick, Hirschau Germany), solids content 59.8%, length-width ratio are 55-60: 1.
Clay (C): 98% particle size is less than the highlighted kaolin water dispersion of 2 microns No.1 (HYDRAGLOSS 90, come from J.M Huber Corp., Have de Grace, the Maryland State, the U.S.), solids content 71%.
Latex: carboxylation of styrene-butadiene latex (DL 966, come from Dow ChemicalCompany), the solids content 50% in the water.
Polyvinyl alcohol: 15% low molecular weight synthesizing polyethylene alcoholic solution (MOWIOL 6/98, comes from Clariant AG, Basel, Switzerland).
Thickener (A): acrylamide-acrylic copolymer anion water-in-oil emulsion (STEROCOL BL comes from BASF, Ludwigshafen, Germany), solids content 37%.
Thickener (B): the non ionic polymer water gaging dissolubility polyethylene oxide polymer of 900,000 molecular weight (POLYOX WSR-1105 comes from Dow Chemical Company) is prepared as the solution of 4% solids content.
Surfactant: the dialkyl sodium sulfosuccinate aqueous solution (AEROSOL OT comes from Cyanamid, Wayne, New Jersey, the U.S.), 75% solids content.
Brightening agent: derived from diaminostilbene, the fluorescent whitening agent of 2-talan-disulfonic acid (TINOPAL ABP/Z comes from Ciba Specialty Chemicals Inc., Ba Saier, Switzerland).
The pH value of pigmented finiss prescription is regulated by adding NaOH solution (10%).If desired, can add the solids content that prescription is regulated in entry.
Coating process
Hereinafter the prescription that is described in detail is applied on paper according to following technical process.Device therefor is a multilayer slip mouthful model curtain coater of being made by Troller Schweizer Engineering (TSE, Murgenthal, Switzerland).The curtain coating device is equipped with by the edge guide plate of thread water lubrication and a vacuum draw equipment, and this equipment is in order to remove the lubricated water in edge of coating paper edge top edges guide plate bottom.In addition, curtain coater is equipped with vacuum draw equipment in order to remove from paper wood from coating curtain top layer, the upstream interface of impact zone air.The height of coating curtain is 300mm.Formulation for coating material carries out degasification before use to remove bubble.In each coated test, the coating weight that obtains according to the known volume flow that coating is sent to the pump of the coating curtain coating leftover of bolt of cloth, translational speed, the density of coating curtain and the width of percent solids and coating curtain of continuous paper base-material under the coating curtain coating leftover of bolt of cloth calculates.
Scraper coated test is as a comparison implemented with a traditional doctor knife coater.Scraper pressure is controlled by the maximums that adjustment anterior angle (head angle) reaches 24 degree.
Method of testing
Brookfield viscosity
Measure viscosity and use Bu Shi RVT viscosimeter (coming from Brookfield EngineeringLaboratories, Inc., Stoughton, Massachusetts, the U.S.).In order to measure viscosity, 600 milliliters samples are injected in 1000 ml beakers, under the speed conditions of 25 ℃ and 100rpm
Measure viscosity.
The parallel-plate viscosity test
Described viscosity uses Physica UDS200 viscosimeter (coming from Paar Physica) to measure.Described sample is under 25 ℃, and using one, to have 0.03 millimeter diameter of measuring the slit be that 50 millimeters parallel-plate is tested.Within two minutes, use logarithm level that 10 grades/ten of shear rate advances shear rate with shear rate from 10s
-1Jump to 100,000s
-13000s
-1With 30,000s
-1Viscosity under the shear rate is determined by the interpolation of measured value.Shearing-multiviscosisty coefficient passes through 30,000s
-1Viscosity under the shear rate is divided by 3000s
-1Viscosity under the shear rate obtains.Shearing-multiviscosisty coefficient value has shearing-multiviscosisty behavior greater than 1 expression.If viscosity presents the rapid rising of viscosity (value added of viscosity value added shear rate greater than 100% is less than 10 times) with respect to the flow curve of shear rate, then described coating is considered to have the retardance behavior of shearing.
The capillary shear viscosity
Shear viscosity utilizes ACAV II capillary viscometer (the ACA system that comes from Finland) to measure.Approximately the sample of 1000cc is placed in the graduated cylinder, and measuring temperature is 25 ℃.Adopting diameter in the measurement is 0.5 millimeter, long 50 millimeters capillary glass tube.Adopt length/diameter can minimize the end impact influence of measurement than the capillary that is 100.It is 100 that 12 logarithm levels of use shear rate record sample viscosity, 000s
-1-1,500,000s
-1If reach 1,500 in shear rate, 000s
-1Before reach maximum the measurement and press (300 crust), measurement then will terminate.Viscosity is calculated by the moving rate curve of the pressure versus flow of measuring and is obtained.ACAV II software is proofreaied and correct the dynamics energy datum.5000,000s
-1Viscosity during shear rate is determined by the interpolation of test data.
Water-retaining property
The water-retaining property of colouring agent for paint is measured by AA-GWR weight water conservation meter (coming from OYGradek, Ab Kauinianen, Finland).Test flume is placed on non-hygroscopic polycarbonate filter (the Nucleopore board with 0.8 micron pore size size, come from Sterico AG, Dietikon, Switzerland) on, this filter is positioned over one and claimed in advance that (Whatman chromatographic paper, 17CHR came from VMR International AG for the blotting paper of weight, Dietikon, Switzerland) on.Be placed on the brace table device also fastening.In test flume, add 10 milliliters of colouring agent for paint then, use plug closes immediately.Pick up counting.The test flume force value is 1 crust after 15 seconds.After finishing in 90 seconds, remove pressure and pipe close.After other 15 seconds, blotting paper is separated from filter membrane.The amount of the liquid that absorbs can be the balance weighing blotting paper acquisition of 0.0001 gram by using an accuracy.Every square metre the absorption liquid scale of construction obtains by the mean value that calculates 3 measured values.
Solidify solids content (immobilization solids content)
Utilize Coesfeld minimum film formation temperature tester (Coesfeld Minimum FilmForming Temperature device) (coming from Coesfeld, Dortmund, Germany) to measure.On the glass plate of one 50 centimeter length, place a metallic plate, thermograde 10 ℃ of other end maintenances when at one end being heated to 50 ℃.One 14 centimetres wide, 0.4 millimeter wetting coating coat of colo(u)r is placed onboard by scraper plate.Dry gradually from the hot junction to cold junction, after 15 minutes, coating sample is taken out with spatula self-desiccation end.The solids content of measuring samples, the mean value of six measured values is taken as the curing solids content.
Coating weight
In each paper coated test, the coating weight that obtains calculate according to known volume flow, speed, the density of coating curtain and the width of percent solids and coating curtain of continuous paper base-material under coating curtain coating stub bar that coating is sent to the pump of coating curtain coating stub bar.
The cratering degree
Determine the cratering degree by visual observation completing combustion sample.Use contains water/isopropyl alcohol (50/50) solution of 10% ammonium chloride.One-side coated paper soaked 30 seconds in above-mentioned solution, and two side coated paper soaked 60 seconds.After removing excessive solution with blotting paper sample is spent the night at air drying.In baking oven, keep carrying out in 3.5 minutes completing combustion down at 225 ℃.Utilize magnifying glass (amplifying 10 times) to calculate cratering on the completing combustion sample in 3 * 3 centimetres of cross sections.The very little spot of not filming with complete circle can not be regarded cratering as; They are considered to the aperture that microvesicle produced that the entrained air in the coating causes.What can not regard cratering equally as is that those ellipses along machine long axis direction (moving direction of paper) are not coated with diaphragm area, and these are by being present in being produced than air pocket of not removing when outgasing in the formulation for coating material.
Coating density
The density of coating curtain layer is determined by the weight of 100 milliliters of coating samples of weighing in specific gravity bottle.
Paper roughness
The roughness on coated paper surface can be used Parker PrinterSurf roughness concentration instrumentation amount.Sample scraps of paper of coated paper are clipped between cork-polyester film pressing plate and the gage outfit, and clamping pressure is 1000 kPas.400 kPas compressed air is supplied to device, measures the leakage of the air between gage outfit and the coated paper surface.The higher higher roughness in measurement numeric representation coated paper surface.
Brightness
Brightness is measured on Zeiss Elrepho 2000.Brightness is measured on a pile scraps of paper according to the ISO2469 standard.Result such as R457.
Opacity
Opacity is measured on Zeiss Elrcpho 2000.Opacity is with black standard (R
0) be to measure on the single-sheet stationery of background and (R on a lot of paper
∝) measure.The result is with R
0/ R
∝* 100% expression.
Granular size
Intermediate value Stokes equivalence spherical particle size and particle size distribution are by X-ray sedimentation (sedigraph) equipment (Sedigraph 5100 Particle Size Analysis System, come from Micromeritics, Norcross, Georgia, the U.S.) measure.Raw materials producers provides the feed particles size used among the embodiment and the particle size distribution data of raw material.
Length-width ratio
Length-width ratio is passed through in " by the definite granules of pigments length-width ratio (Aspect Ratiosof Pigment Particles Determined by Different) of the differential method ",
Nordic Pulp and Paper Research Journal, Vol.15, No.3/2000, the electronic microscope image analytical method of putting down in writing among the pp.221-230 records.
Embodiment 1
Said components is mixed the clay that has used high-aspect-ratio with demonstration according to the amount that provides in the table 1.
Table 1
500,000s
-1The viscosity of the coating under the shear rate in the slit 2 has exceeded observation scope, the operation existing problems (greater than 50mPas) on knife type coater, and the shear-thickening coefficient is greater than 1.2.
| Slit 1 | Slit 2 | |
| Carbonate (A) | ????100 | |
| Clay (B) | ????100 | |
| Latex | ????13 | ????13 |
| Polyvinyl alcohol | ????1 | ????3.5 |
| Surfactant | ????0.4 | ????0.2 |
| Brightening agent | ????1 | |
| PH | ????8.5 | ????8.6 |
| Solids content (percentage) | ????60.1 | ????55.7 |
| Density (g/cm 3) | ????1.51 | ????1.43 |
| Brookfield viscosity [mPas] | ????120 | ????755 |
| 3,000s -1The time viscosity [mPas] | ????29.9 | ????114 |
| 30,000s -1The time viscosity [mPas] | ????13.5 | ????150 |
| 500,000s -1The time viscosity [mPas] | ????13.6 | ????57.9 |
| The shear-thickening coefficient | ????0.45 | ????1.32 |
Test speed and coating weight to each layer among the embodiment 1 are listed in the table 2.Used body paper is that surface roughness is a wooden paper 4.3 microns contain.
Table 2
| Speed [m/min] | Slit 1 coating weight g/m 2(doing) | Slit 2 coating weight g/m 2(doing) |
| ????1000 | ????2 | ????6 |
| ????1000 | ????2 | ????8 |
| ????1200 | ????2 | ????8 |
| ????1500 | ????2 | ????8 |
A dyed layer (slit 1) and paper adjacency.The second layer is added simultaneously with slit 2, and this one deck comprises the clay of high-aspect-ratio.Layered coating in table 2 under the listed all situations no operation problem ground successfully be coated with.
Embodiment 2
Component mentioned above has been used calcined clay by the amount mixing that provides in the table 3 to show.
Table 3
| Slit 1 | Slit 2 | |
| Carbonate (A) | ????100 | |
| Clay | ????100 | |
| Latex (A) | ????13 | ????13 |
| Polyvinyl alcohol | ????1 | ????3.5 |
| Surfactant | ????0.4 | ????0.2 |
| Brightening agent | ????1 | |
| PH | ????8.5 | ????8.6 |
| Solids content (percentage) | ????60.1 | ????47.9 |
| Density (g/cm 3) | ????1.51 | ????1.36 |
| Brookfield viscosity [mPas] | ????120 | ????470 |
| 3,000s -1The time viscosity [mPas] | ????29.9 | ????30.7 |
| 30,000s -1The time viscosity [mPas] | ????13.5 | ????47.6 |
| 500,000s -1The time viscosity [mPas] | ????13.6 | ????105.2 |
| The shear-thickening coefficient | ????0.45 | ????1.55 |
500,000s
-1The viscosity of the coating under the shear rate in the slit 2 has exceeded observation scope, and there is very big problem (greater than 100mPas) in the operation on knife type coater, and the shear-thickening coefficient is greater than 1.5.
Speed of each layer and coating weight are listed in the table 4 among the embodiment 2.Used body paper is that surface roughness is a wooden paper 4.3 microns contain.
Table 4
| Speed [m/min] | Slit 1 coating weight g/m 2(doing) | Slit 2 coating weight g/m 2(doing) |
| ????1000 | ????2 | ????6 |
| ????1000 | ????2 | ????8 |
| ????1200 | ????2 | ????6 |
| ????1200 | ????2 | ????8 |
A dyed layer (slit 1) and paper adjacency.The second layer is added simultaneously with slit 2, and this one deck comprises calcined clay.Layered coating in table 4 under the listed all situations no operation problem ground successfully be coated with.Be 8g/m with the clay (A) in the prescription of slit in clay (C) substitution list 32 and with the single coating weight of scraper coating
2Laboratory sample compare, the sample of the coated paper that obtains under first test condition in table 4 has improved opacity (92.6 pairs 90.4) and brightness (80.4 pairs 73.7) significantly
Embodiment 3
The method that replaces a part of polyvinyl alcohol (PVOH) repetition embodiment 1 in the top layer (slit 2) with thickener.In comparative experiments used thickener because of its to the adaptability of high speed blade coating with under high coating speed, can provide the performance of coating curtain coating layer of no cratering selected.In addition, the amount of the polyvinyl alcohol in bottom (slit 1) is added to two parts, and brightening agent is removed (slit 2) from top layer.Coating composition is mixed by the amount that provides in the table 5.
Table 5
| Slit 1 | Slit 2 | |
| Carbonate (A) | ????100 | |
| Clay (B) | ????100 | |
| Latex | ????13 | ????13 |
| Polyvinyl alcohol | ????2 | ????1.0 |
| Thickener (A) | ????0.2 | |
| Surfactant | ????0.4 | ????0.2 |
| PH | ????8.5 | ????8.6 |
| Solids content (percentage) | ????60.3 | ????55.8 |
| Density (g/cm 3) | ????1.51 | ????1.43 |
| ABO water retention rate (g/m 2) | ????NM * | ????76 |
| Brookfield viscosity [mPas] | ????350 | ????740 |
| 3,000s -1The time viscosity [mPas] | ????NM | ????153 |
| 30,000s -1The time viscosity [mPas] | ????NM | ????214 |
| 500,000s -1The time viscosity [mPas] | ????NM | ????96 |
| The shear-thickening coefficient | ????NM | ????1.39 |
(
*NM=does not measure)
Coating in the slit 2 is 500,000s
-1Viscosity under the shear rate has exceeded observation scope, operation difficulty (greater than 75mPas) on knife type coater, and the shear-thickening coefficient is greater than 1.2.
Each layer coating weight in the slit 1 is 1.5g/m
2(doing), each layer coating weight in the slit 2 is 6.5g/m
2(doing).Under the coating speed of 1250m/min and 1500m/min, total coating weight of layered coating is 8g/m
2(doing).Used body paper is that a kind of surface roughness is 4.8 microns 35g/m
2Contain wooden paper.The coating that is coated with under 1250m/min speed has produced the coating of a no cratering, and the coating that is coated with under 1500m/min speed has produced a coating that is close to no cratering not having other operation problem.This just proves with method of the present invention can easily will have the coating of high-aspect-ratio pigment and high shear viscosity to be coated with high coating speed on curtain coater.
Comparative experiments A
Attempting containing the coating (slit 2 of embodiment 3) of high-aspect-ratio pigment coats on the same body paper used among the embodiment 3 with spraying knife type coater (jet applicator blade coater).It is impossible using this spray equipment to carry out suitable coating composition under the coating speed of 1250m/min, because when coating is got on the base-material, coating will be gone out from paper substrate material upper deflecting.
Comparative experiments B
Repeat the method for Comparative Example A An, different is with the coating compound that provides in the table 6.This coating composition is represented the blending of the pigment composition in two kinds of coating (slit 1 and 2) that embodiment 3 uses.Polyvinyl alcohol, surfactant, the amount used with the amount and the top layer (slit 2) among the embodiment 3 of thickener is identical.
Table 6
| Carbonate (A) | ????19 |
| Clay (B) | ????81 |
| Latex | ????13 |
| Polyvinyl alcohol | ????1.0 |
| Thickener (A) | ????0.2 |
| Surfactant | ????0.2 |
| PH | ????8.6 |
| Solids content (percentage) | ????59.2 |
| Density (g/cm 3) | ????1.46 |
| ABO water retention rate (g/m 2) | ????74 |
| Brookfield viscosity [mPas] | ????1690 |
| 3,000s -1The time viscosity [mPas] | ????215 |
| 30,000s -1The time viscosity [mPas] | ????294 |
| 500,000s -1The time viscosity [mPas] | ????110 |
| The shear-thickening coefficient | ????1.37 |
Is 8.3g/m with the spraying knife type coater with total coating weight
2The coating of (doing) is coated on the same body paper used among the embodiment 3 with the speed of 1250m/min.Measuring scraper is the thick scraper with 45 degree oblique angles of a kind of 0.4mm, has the scraper load (anterior angle) of one 12.1 degree during running.This scraper demonstrates wet coating diffusion (spreading 30g coating 2 minute running time) extremely.In addition, have many not coated jumpings on the paper wood and be coated with the district.Spend when the scraper oblique angle becomes 40, scraper can turn round cleanly so, and (coating weight when the anterior angle maximum of 24 degree is 8.3g/m but the scraper load is very high
2).These scraper conditions will cause the frequent base-material fracture and the quick wearing and tearing of scraper, thereby cause the long parking of unacceptable production equipment.
When using the scraper coating at the thick 45 degree oblique angles of 0.4mm under the coating speed of 1500m/min, existing operation problem is even more serious.Reach 8.0g/m
2Total required scraper pressure (anterior angle) of coating weight (doing) is 22.7 degree.At this moment it is can not be received that coating diffusion very obvious (the coating diffusion of 37.5g is arranged after the running in 2 minutes) and jumping are coated with degree.
Embodiment 4
Repeat the method for embodiment 2, different is to replace a part of polyvinyl alcohol (PVOH) with thickener in top layer coating (slit 2).In comparative experiments used thickener because of its to the adaptability of high speed blade coating with under high coating speed, can provide the performance of no cratering coating curtain selected.In addition, the amount of the polyvinyl alcohol in bottom (slit 1) is added to two parts, removes brightening agent in the top layer (slit 2).Coating composition is mixed by the amount that provides in the table 7.
Table 7
| Slit 1 | Slit 2 | |
| Carbonate (A) | ????100 | |
| Clay (A) | ??100 | |
| Latex | ????13 | ??13 |
| Polyvinyl alcohol | ????2 | ??2.0 |
| Thickener (A) | ??0.2 | |
| Surfactant | ????0.4 | ??0.2 |
| PH | ????8.5 | ??8.6 |
| Solids content (percentage) | ????60.3 | ??48.8 |
| Density (g/cm 3) | ????1.51 | ??1.38 |
| Brookfield viscosity [mPas] | ????350 | ??410 |
| 3,000s -1The time viscosity [mPas] | ????NM * | ??595 |
| 30,000s -1The time viscosity [mPas] | ????NM | Too high can't the measurement |
| 500,000s -1The time viscosity [mPas] | ????NM | ??137 |
| The shear-thickening coefficient | ????NM | Can't calculate |
| Shear the retardance behavior | ????NM | Have |
(
*NM=does not measure)
Coating in the slit 2 is 500,000s
-1Viscosity under the shear rate has exceeded observation scope, operation difficulty (greater than 100mPas) on knife type coater, and coating shows the shear-thickening behavior in addition.
The coating weight of coating each layer under the coating speed of 1500m/min is 1.5g/m in the slit 1
2(doing), in the slit 2 is 6.5g/m
2(doing).Used body paper is that a kind of surface roughness is 4.8 microns 35g/m
2Contain wooden paper.Under the coating speed of 1500m/min, layered coating is with 8g/m
2Total coating weight of (doing) is applied and do not have other operation problem a coating of almost not having cratering can be provided.This just proves can easily be coated with to have the coating of shearing the retardance behavior on curtain coater.
Comparative experiments C
The coating (slit 2 among the embodiment 4) that will contain calcined clay pigment with the spraying knife type coater of the scraper that the thick miter angle of 0.4mm is housed coat with embodiment 4 on the used same body paper.Under the coating speed of 1500m/min, reach 8.4g/m
2(doing) required scraper load (anterior angle) is 21.4 degree and scraper running cleaning.This just proves the scraper load that the calcined clay pigment requirement is high relatively.
Comparative experiments D
Repeat the method for comparing embodiment C, different is with the coating compound that provides in the table 8.This coating composition shows as the blending of the pigment component in two kinds of coating (slit 1 and 2) that embodiment 4 uses.The used amount of top layer is identical among the amount of polyvinyl alcohol, surfactant and thickener and the embodiment 4.Under the coating speed of 1500m/min, reach 8.0g/m
2(doing) required scraper load (anterior angle) is 22.4 degree and scraper running cleaning.
Table 8
| Carbonate (A) | ????19 |
| Clay (A) | ????81 |
| Latex | ????13 |
| Polyvinyl alcohol | ????2.0 |
| Thickener (A) | ????0.2 |
| Surfactant | ????0.2 |
| PH | ????8.6 |
| Solids content (percentage) | ????51.7 |
| Density (g/cm 3) | ????1.41 |
| Brookfield viscosity [unit] | ????420 |
| 3,000s -1The time viscosity [mPas] | ????523 |
| 30,000s -1The time viscosity [mPas] | Too high can't the measurement |
| 500,000s -1The time viscosity [mPas] | ????124 |
| The shear-thickening coefficient | Can't calculate |
| Shear the retardance behavior | Have |
Embodiment 5
Repeat the program of embodiment 1, different is with the prescription in the table 9.This embodiment shows to have used with grinding calcium carbonate commonly used and compares the engineering calcium carbonate pigment with narrow particle size distribution.Low water retention rate of coating and the low solids content of solidifying have been given at the highly filled formulation for coating material that has low amount of thickener down.
Table 9
| Slit 1 | Slit 2 | |
| Carbonate (A) | ????100 | |
| Carbonate (C) | ????100 | |
| Latex | ????13 | ????11 |
| Polyvinyl alcohol | ????1.0 | ????0.5 |
| Thickener (A) | ????0.17 | |
| Surfactant | ????0.4 | ????0.2 |
| PH | ????8.5 | ????8.6 |
| Solids content (percentage) | ????60.0 | ????67.2 |
| Density (g/cm 3) | ????1.51 | ????1.38 |
| Water retention rate (g/m 2) | ????NM * | ????133 |
| Solidify solids content (percentage) | ????NM | ????82.3 |
| Brookfield viscosity [mPas] | ????240 | ????1160 |
| 3,000s -1The time viscosity [mPas] | ????NM | ????162 |
| 30,000s -1The time viscosity [mPas] | ????NM | ????141 |
| 500,000s -1The time viscosity [mPas] | ????NM | ????127 |
| The shear-thickening coefficient | ????NM | ????0.87 |
(
*NM=does not measure)
Colouring agent for paint in the slit 2 is 500,000s
-1Viscosity under the shear rate has exceeded observation scope, moves very difficulty (greater than 100mPas) on knife type coater.
The coating weight of each layer in the slit 1 is 1.5g/m
2(doing) is 6.5g/m in the slit 2
2(doing).Total coating weight is 8g/m
2The layered coating of (doing) is applied under the coating speed of 1250m/min to be 4.8 microns 35g/m in surface roughness
2Contain on the wooden paper.This coating does not have cratering and coating does not have other operation problem.This can easily coat the coating with high rate of water loss and rapidly-curable in the substrate with the curtain coating method with regard to proof.
Embodiment 6
Repeat the method for embodiment 5, different is replaces with the coating in the slit 1 identical with coating in the slit 2 but solids content is diluted to 58.3% coating.This just causes a multi-layer coated act of wherein two-layer composition identical, just different on solids content.This applied coating shows no cratering and does not have other operational defect.
Comparative experiments E
Use the coating (slit 2 of embodiment 5) that the trial of spraying knife type coater will contain engineering carbonate to coat on the same body paper used among the embodiment 5.Under the maximum scraper pressure (anterior angle) of 24 degree, coating weight is 1.1g/m
2(doing).This coating is diluted to 65.5% solids content and has the 890mPas brookfield viscosity, 500, and 000s
-1Shear rate under have the viscosity of 107mPas and 137 water retention rate.Coating weight under scraper pressure maximum (anterior angle=24 degree) situation is 9.3g/m
2(doing).Used coating further is diluted to 64.3% solids content and is had the 730mPas brookfield viscosity, 500, and 000s
-1Shear rate under have the viscosity of 88mPas and 146 water retention rate.This coating can reach 8.3g/m
2The coating weight of (doing), but scraper pressure is not a stationary value.Be to keep coating weight, scraper pressure (anterior angle) must be increased to maximum constantly, has exceeded 8g/m at coating during this period of time
2The coating weight desired value of (doing).In addition, the coating sediment of Ganing is deposited in blade tip (producing 3.3g 3.75 minutes running time).These " grooves " of doing are very big and will finally cause striped on the surface of coated paper.The relatively poor service ability of this coating is owing to the curing of its fast rate of water loss and the coating under scraper.
Embodiment 7
The described component of preamble is mixed with the amount that provides in the table 10, to set forth the use of a kind of coarse carbonate pigment carbonate D.This carbonate pigment contains the particle of the diameter of 2 weight % greater than 12 μ m.This pigment can not be coated with and not produce serious striped with knife type coater, and this is the thickness that approaches wet coating because of its contained oarse-grained diameter.
Table 10
| Slit 1 | Slit 2 | Slit 3 | |
| Carbonate (A) | ????25 | ????30 | |
| Carbonate (D) | ????100 | ????70 | |
| Clay (C) | ????75 | ||
| Latex | ????13 | ????10 | ????11 |
| Polyvinyl alcohol | ????1.0 | ????0.8 | ????0.8 |
| Thickener (B) | ????0.2 | ????0.15 | ????0.07 |
| Surfactant | ????0.4 | ????0.2 | |
| PH | ????9.3 | ????8.6 | ????8.6 |
| Solids content (percentage) | ????60.1 | ????70.0 | ????62.3 |
| Density (g/cm 3) | ????1.50 | ????1.67 | ????1.54 |
| Brookfield viscosity [mPas] | ????980 | ????210 | ????1120 |
Thickener (B) is added in the coating to prevent cratering.The test of each coating is listed in the table 11 with speed and coating weight among the embodiment 7.Used body paper is that surface roughness is 8.5 microns 75g/m
2Nothing wood paper.
Table 11
| Speed [m/min] | Slit 1 coating weight g/m 2(doing) | Slit 2 coating weight g/m 2(doing) | Slit 3 coating weight g/m 2(doing) |
| ???1200 | ????1.5 | ????5.5 | ????3 |
| ???1200 | ????2.5 | ????12.5 | ????5 |
Described coating does not have cratering and does not have other operation problem.Total coating weight is 10g/m
2It is that not calendering surface and the surface roughness of 5.52 μ m is the calendering surface of 2.1 μ m that the coating of (doing) has surface roughness.Total coating weight is 20g/m
2It is that not calendering surface and the surface roughness of 3.95 μ m is the calendering surface of 1.3 μ m that the coating of (doing) has surface roughness.This just proof can easily be coated on the layered coating that uses coarse pigment in the main dope layer with curtain coater, and can obtain and the paper of the pigment application that usefulness is thinner is compared similar smooth surface.
Claims (31)
1. the coated paper of a production except that sensitive paper or the method for cardboard, it may further comprise the steps:
(a) form one comprise one deck at least flow freely the coating curtain, wherein form composition that one deck at least flows freely coating curtain layer at 25 ℃ and 500,000s
-1Shear rate under have 50mPas at least shear viscosity and
(b) described coating curtain is contacted with the continuous body paper or the web substrate of cardboard.
2. method according to claim 1 is characterized in that one deck at least in the step (a) flows freely coating curtain layer and has the shear viscosity of 75mPas at least, preferred 100mPas at least, most preferably 125mPas at least.
3. the coated paper of a production except that sensitive paper or the method for cardboard, it may further comprise the steps:
(a) form one comprise one deck at least flow freely the coating curtain, wherein form the composition that one deck at least flows freely coating curtain layer and comprise at least a pigment, the shape of described pigment and structure are being lower than 500,000s
-1Shear rate under destroyed and
(b) described coating curtain is contacted with the continuous body paper or the web substrate of cardboard.
4. the coated paper of a production except that sensitive paper or the method for cardboard, it may further comprise the steps:
(a) form one comprise one deck at least flow freely the coating curtain, wherein form the shear-thickening coefficient value that one deck at least flows freely the composition of coating curtain layer and be at least 1.2 at 25 ℃, this shear-thickening coefficient is defined as 30,000s
-1Viscosity under the shear rate and 3,000s
-1The ratio of the viscosity under the shear rate and
(b) described coating curtain is contacted with the continuous body paper and the web substrate of cardboard.
5. according to the described method of aforementioned each claim, it is characterized in that the coating curtain that flows freely in the step (a) is that multilayer flows freely the coating curtain.
6. method according to claim 5 is characterized in that the coating curtain that flows freely in the step (a) comprises the top layer of guaranteeing printability.
7. according to claim 5 or 6 described methods, it is characterized in that the coating curtain that flows freely in the step (a) comprises at least three layers.
8. according to the described method of aforementioned each claim, it is characterized in that the one deck at least that flows freely coating curtain layer in the step (a) comprises at least a pigment.
9. method according to claim 8 is characterized in that described pigment is selected from clay, kaolin, calcined clay, co-structuredization pigment, talcum, calcium carbonate, titanium dioxide, satin white, synthetic polymer pigment, zinc oxide, barium sulfate, gypsum, silica, gibbsite, mica, synthetic magadiite and diatomite.
10. according to the described method of aforementioned each claim, it is characterized in that the one deck at least that flows freely coating curtain layer in the step (a) comprises the pigment that at least a length-width ratio was at least 1.5: 1.
11., it is characterized in that the one deck at least that flows freely coating curtain layer in the step (a) comprises adhesive according to the described method of aforementioned each claim.
12. method according to claim 11 is characterized in that described adhesive is selected from styrene-butadiene latex, styrene-acrylate latex, styrene-butadiene-acrylonitrile latex, styrene-acrylate-acrylonitrile latex, styrene-butadiene-acrylate-acrylonitrile latex, styrene-maleic anhydride latex, styrene-acrylate-maleic anhydride latex, polysaccharide, protein, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, cellulose derivative and their mixture.
13., it is characterized in that the one deck at least that flows freely coating curtain layer in the step (a) has the solids content of at least 30 weight % according to the described method of aforementioned each claim, be preferably at least 40 weight %, most preferably be at least 50 weight %.
14., it is characterized in that the coating curtain that flows freely in the step (a) has the solids content of at least 40 weight % according to the described method of aforementioned each claim, be preferably at least 45 weight %, most preferably be at least 50 weight %.
15., it is characterized in that the one deck at least that flows freely coating curtain layer in the step (a) comprises at least a fluorescent whitening agent according to the described method of aforementioned each claim.
16., it is characterized in that the one deck at least that flows freely coating curtain layer in the step (a) comprises at least a surfactant according to the described method of aforementioned each claim.
17., it is characterized in that the coating curtain that flows freely in the step (a) comprises at least 4 layers according to the described method of aforementioned each claim, be preferably at least 5 layers, and more preferably at least 6 layers.
18., it is characterized in that the one deck at least that flows freely coating curtain layer in the step (a) has less than 10g/m according to the described method of aforementioned each claim
2The coating weight dry weight, preferably less than 8g/m
2, most preferably less than 6g/m
2
19., it is characterized in that the both not also not calenderings in advance of pre-coating of continuous web substrate in the step (b) according to the described method of aforementioned each claim.
20. according to the described method of aforementioned each claim, it is characterized in that the continuous web substrate in the step (b) has the base-material speed of 300m/min at least, preferred 400m/min at least, most preferably 500m/min at least.
21. according to the described method of aforementioned each claim, the every Gram Mass that it is characterized in that the continuous web substrate in the step (b) is 20-350g/m
2
A 22. coated paper or cardboard that makes by the described method of aforementioned each claim.
23. the coated paper of a production except that sensitive paper or the method for cardboard, it may further comprise the steps:
(a) form one comprise one deck at least flow freely the coating curtain, wherein form a composition that one deck at least flows freely coating curtain layer have the retardance behavior of shearing and
(b) described coating curtain is contacted with the continuous body paper and the web substrate of cardboard.
24. the coated paper of a production except that sensitive paper or the method for cardboard, it may further comprise the steps:
(a) form one comprise one deck at least flow freely the coating curtain, wherein form difference that one deck at least flows freely its paint solidification solids content of composition of coating curtain layer and coating applying solid content less than 15 and
(b) described coating curtain is contacted with the continuous body paper and the web substrate of cardboard.
25. the coated paper of a production except that sensitive paper or the method for cardboard, it may further comprise the steps:
(a) form one comprise one deck at least flow freely the coating curtain, wherein form pigment in the composition that one deck at least flows freely coating curtain layer have at least 2 microns particle size and
(b) described coating curtain is contacted with the continuous body paper and the web substrate of cardboard.
26. the diameter that method according to claim 25, the described pigment in the wherein said coating composition comprise at least 0.5 weight % is greater than 10 microns particle.
27. according to the described method of aforementioned each claim, wherein said continuous web substrate has 800m/min and the preferred speed of 1000m/min at least at least.
28. according to the described method of aforementioned each claim, wherein said coating curtain forms by a clearance type mouth mould.
29. according to the described method of aforementioned each claim, wherein said coating curtain forms by mouthful mould that slides.
30. according to the described method of aforementioned each claim, wherein the described coating curtain of one deck layer comprises poly(ethylene oxide) at least.
31. according to the described method of aforementioned each claim, wherein said coating curtain comprises poly(ethylene oxide) in its boundary layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2002/033114 WO2004035931A1 (en) | 2002-10-15 | 2002-10-15 | Process for making coated paper or paperboard |
| USPCT/US02/33114 | 2002-10-15 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101085863A Division CN101063282B (en) | 2002-10-15 | 2003-10-15 | Process for making coated paper or paperboard |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1510214A true CN1510214A (en) | 2004-07-07 |
Family
ID=32092101
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101085863A Expired - Fee Related CN101063282B (en) | 2002-10-15 | 2003-10-15 | Process for making coated paper or paperboard |
| CNA2003101156894A Pending CN1510214A (en) | 2002-10-15 | 2003-10-15 | Method for producing coated paper or paper board |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101085863A Expired - Fee Related CN101063282B (en) | 2002-10-15 | 2003-10-15 | Process for making coated paper or paperboard |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1416088B1 (en) |
| CN (2) | CN101063282B (en) |
| AT (1) | ATE458859T1 (en) |
| AU (1) | AU2002335832A1 (en) |
| BR (1) | BR0304592A (en) |
| CA (1) | CA2444925C (en) |
| DE (1) | DE60331398D1 (en) |
| WO (1) | WO2004035931A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101646823B (en) * | 2007-01-31 | 2012-07-04 | 阿乔·韦京斯精细纸业有限公司 | Offset-printable coated white paper having a high fluorescence intensity and method for producing same |
| CN103459721A (en) * | 2011-03-29 | 2013-12-18 | 日本制纸株式会社 | Coated white paperboard and method for manufacturing same |
| CN109790686A (en) * | 2016-08-08 | 2019-05-21 | 维实洛克Mwv有限责任公司 | Compost cardboard with oil resistant, grease resistance and moisture-proof |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1249533A1 (en) | 2001-04-14 | 2002-10-16 | The Dow Chemical Company | Process for making multilayer coated paper or paperboard |
| US7473333B2 (en) | 2002-04-12 | 2009-01-06 | Dow Global Technologies Inc. | Process for making coated paper or paperboard |
| WO2005028750A1 (en) * | 2003-09-16 | 2005-03-31 | Voith Paper Patent Gmbh | Method and device for producing decorative paper and the use thereof |
| DE10343273A1 (en) * | 2003-09-17 | 2005-04-21 | Voith Paper Patent Gmbh | Coating machine for applying at least one color with a high solids content |
| DE102004062119A1 (en) * | 2004-12-23 | 2006-07-13 | Voith Paper Patent Gmbh | Method of applying a multiple layer directly to a moving paper, board or other fibrous web |
| DE102004062120A1 (en) * | 2004-12-23 | 2006-07-13 | Voith Paper Patent Gmbh | Method and apparatus for treating a moving paper, board or other fibrous web |
| PL1762377T3 (en) | 2005-09-07 | 2008-12-31 | Alcan Tech & Management Ltd | A method for the preparation of a laminate |
| EP1800857A1 (en) * | 2005-12-21 | 2007-06-27 | Alcan Technology & Management Ltd. | Curtain coating method |
| FI120206B (en) * | 2006-10-03 | 2009-07-31 | Metso Paper Inc | Method for Determining the Coating Quantity of Single Coating Layers in Multi-Layer Curtain Coating |
| JP2008173577A (en) * | 2007-01-19 | 2008-07-31 | Voith Patent Gmbh | Curtain coater |
| CN110344282A (en) | 2011-09-15 | 2019-10-18 | 英默里斯颜料公司 | Kaolinic composition and correlation technique comprising the polymer treatment with styrene-based |
| CN106634350B (en) * | 2016-12-23 | 2019-01-15 | 煤科集团杭州环保研究院有限公司 | Aqueous low viscosity background color showering paint and its full aqueous insulation decoration integrated board facing production technology |
| WO2020203616A1 (en) | 2019-03-29 | 2020-10-08 | 日本製紙株式会社 | Method for manufacturing paper-making barrier substrate |
| CN111576084B (en) * | 2020-06-09 | 2022-06-14 | 广东彩乐智能包装科技有限公司 | Fluorine-free waterproof oil-proof food-grade coating and preparation method thereof |
| US11549216B2 (en) | 2020-11-11 | 2023-01-10 | Sappi North America, Inc. | Oil/grease resistant paper products |
| CN113529492B (en) * | 2021-07-16 | 2023-02-03 | 东北电力大学 | Preparation method of hydrophobic wallpaper base paper based on diatomite |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3508947A (en) * | 1968-06-03 | 1970-04-28 | Eastman Kodak Co | Method for simultaneously applying a plurality of coated layers by forming a stable multilayer free-falling vertical curtain |
| US3632374A (en) | 1968-06-03 | 1972-01-04 | Eastman Kodak Co | Method of making photographic elements |
| CH591902A5 (en) * | 1975-05-14 | 1977-10-14 | Ciba Geigy Ag | |
| CH613879A5 (en) * | 1976-03-30 | 1979-10-31 | Ciba Geigy Ag | |
| JPS532108A (en) | 1976-06-28 | 1978-01-10 | Fuji Photo Film Co Ltd | Method of producing pressure sensitixed copy sheets |
| JP2960127B2 (en) * | 1990-08-17 | 1999-10-06 | 三菱製紙株式会社 | Coated paper for rotary offset printing |
| JP3222221B2 (en) * | 1992-11-09 | 2001-10-22 | 三菱製紙株式会社 | Pigment coated paper for printing and method for producing the same |
| JPH07119083A (en) * | 1993-07-19 | 1995-05-09 | Mitsubishi Paper Mills Ltd | Pigment-coated paper and its production |
| JP3222293B2 (en) * | 1993-12-13 | 2001-10-22 | 三菱製紙株式会社 | Pigment coated paper for printing and method for producing the same |
| JP3257745B2 (en) * | 1994-04-27 | 2002-02-18 | 三菱製紙株式会社 | Coated paper for lightweight printing and method for producing the same |
| KR19980701874A (en) * | 1995-02-02 | 1998-06-25 | 워렌 리차드 보비 | Method and apparatus for applying a thin fluid coated stripe |
| JPH10328613A (en) | 1997-06-02 | 1998-12-15 | Mitsubishi Paper Mills Ltd | Coating method |
| SE515824C2 (en) * | 2000-01-26 | 2001-10-15 | Tetra Laval Holdings & Finance | Method for manufacturing a multilayered packaging laminate by wet coating, as well as laminates made according to the procedure |
| GB0002479D0 (en) * | 2000-02-04 | 2000-03-22 | Eastman Kodak Co | Method of curtain coating |
| DE10057729A1 (en) * | 2000-11-22 | 2002-05-23 | Voith Paper Patent Gmbh | Web coating station, has two applicators, to deliver the coatings as falling curtains, with different coating media and a structured gap between the strike points of each at the moving substrate for the overlaid layers |
| US20020114933A1 (en) * | 2000-12-28 | 2002-08-22 | Gould Richard J. | Grease masking packaging materials and methods thereof |
| ATE368149T1 (en) * | 2001-02-16 | 2007-08-15 | Voith Patent Gmbh | METHOD FOR PRODUCING COATED PAPER OR CARDBOARD&X9; |
| EP1249533A1 (en) * | 2001-04-14 | 2002-10-16 | The Dow Chemical Company | Process for making multilayer coated paper or paperboard |
-
2002
- 2002-10-15 AU AU2002335832A patent/AU2002335832A1/en not_active Abandoned
- 2002-10-15 WO PCT/US2002/033114 patent/WO2004035931A1/en not_active Application Discontinuation
-
2003
- 2003-10-15 AT AT03023325T patent/ATE458859T1/en active
- 2003-10-15 EP EP03023325A patent/EP1416088B1/en not_active Expired - Lifetime
- 2003-10-15 CA CA2444925A patent/CA2444925C/en not_active Expired - Fee Related
- 2003-10-15 CN CN2007101085863A patent/CN101063282B/en not_active Expired - Fee Related
- 2003-10-15 CN CNA2003101156894A patent/CN1510214A/en active Pending
- 2003-10-15 DE DE60331398T patent/DE60331398D1/en not_active Expired - Lifetime
- 2003-10-15 BR BR0304592-7A patent/BR0304592A/en active Search and Examination
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101646823B (en) * | 2007-01-31 | 2012-07-04 | 阿乔·韦京斯精细纸业有限公司 | Offset-printable coated white paper having a high fluorescence intensity and method for producing same |
| CN103459721A (en) * | 2011-03-29 | 2013-12-18 | 日本制纸株式会社 | Coated white paperboard and method for manufacturing same |
| CN109790686A (en) * | 2016-08-08 | 2019-05-21 | 维实洛克Mwv有限责任公司 | Compost cardboard with oil resistant, grease resistance and moisture-proof |
| CN109790686B (en) * | 2016-08-08 | 2022-03-15 | 维实洛克Mwv有限责任公司 | Compostable paperboard with oil, grease and moisture resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1416088A3 (en) | 2004-05-12 |
| BR0304592A (en) | 2004-08-31 |
| WO2004035931A1 (en) | 2004-04-29 |
| EP1416088A2 (en) | 2004-05-06 |
| ATE458859T1 (en) | 2010-03-15 |
| CN101063282B (en) | 2011-11-23 |
| DE60331398D1 (en) | 2010-04-08 |
| CA2444925C (en) | 2012-01-03 |
| CA2444925A1 (en) | 2004-04-15 |
| AU2002335832A1 (en) | 2004-05-04 |
| EP1416088B1 (en) | 2010-02-24 |
| CN101063282A (en) | 2007-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1510214A (en) | Method for producing coated paper or paper board | |
| EP1794365B1 (en) | Multi-layer coated products and curtain coating process for same | |
| JP4246497B2 (en) | Method for producing multilayer coated paper or multilayer coated paperboard | |
| EP2814890B1 (en) | Pigment compositions | |
| US7364774B2 (en) | Method of producing a multilayer coated substrate having improved barrier properties | |
| US7473333B2 (en) | Process for making coated paper or paperboard | |
| JP2004148307A (en) | Method of manufacturing multilayer coated support improved in barrier properties | |
| CN1098756A (en) | The pigment that is used for coating composition for printing paper | |
| JP4943627B2 (en) | Method for producing coated substrate | |
| CN101680192A (en) | Paper coating composition, coated paper and method | |
| US20030194501A1 (en) | Method of producing a coated substrate | |
| KR100990793B1 (en) | Copolymer Latex for Noncontact Coating and Composition Comprising the Same, and Coated Paper and Method for Production Thereof | |
| JP2009529076A (en) | Method for producing a substrate coated once and / or several times | |
| CN107407055A (en) | Extensible coating | |
| JPH06294099A (en) | Pigment-coated paper for printing and its production | |
| CN104169496A (en) | Coated white paperboard and method for producing same | |
| JPH05117996A (en) | Production of pigment-coated paper for printing | |
| JP2005120502A (en) | Method for producing coated paper or paperboard | |
| CN108349270A (en) | The printed medium of coating | |
| JP2012016704A (en) | Method of manufacturing coated paper or cardboard | |
| JP2014040698A (en) | Method of making coated paper or paperboard | |
| JPH11336000A (en) | Coated printing paper and its production | |
| JP2010174407A (en) | Method for producing coated paper for printing use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination |