CN100400748C - Method for producing coating groundmass - Google Patents
Method for producing coating groundmass Download PDFInfo
- Publication number
- CN100400748C CN100400748C CNB200310115663XA CN200310115663A CN100400748C CN 100400748 C CN100400748 C CN 100400748C CN B200310115663X A CNB200310115663X A CN B200310115663XA CN 200310115663 A CN200310115663 A CN 200310115663A CN 100400748 C CN100400748 C CN 100400748C
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- Prior art keywords
- curtain
- described method
- multilayer
- coating
- component
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- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical class O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/46—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
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
- B05D1/305—Curtain coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/22—Paper or cardboard
Abstract
The present invention refers to a method of producing a coated substrate comprising the steps of: a) forming a free flowing curtain, the curtain having at least one component capable of reacting, and b) contacting the curtain with a continuous web substrate.
Description
Technical field
The present invention relates to a kind of method of producing coating substrate.More particularly, the present invention relates to a kind of method of producing coated paper or cardboard.
Background technology
Usually coating composition is applied to described matrix, and in the manufacturing of coating substrate, coating process for example has that scraper plate is coated with formula, and scraping article is coated with formula, contrary roller coat formula.Linear velocity may surpass 1000m/min.Any one or these all methods generally all are that the continuous matrix that moves of giving provides coating.
Yet all there are some problems in itself in each above-mentioned application process, thereby causes the with low quality of coating surface.Using scraper plate to be coated with under the situation of formula coating process, the particulate deposits below blade can cause that striped is arranged in the coating, and this will reduce the quality of coated paper or cardboard.In addition, for the high pressure that the coating weight that makes scraper plate obtain expection must provide, be a weight to matrix, can cause the breakage of base-material net, thereby cause the reduction of production efficiency.And because colored paint has high abrasion, in order to keep the smooth of top layer of filming, scraper plate must regularly replace.Equally, the distribution of coating on paper or cardboard substrates surface is subjected to the irregular influence of stromal surface.The coating skewness of coating the surface of paper or cardboard can cause the surface spot or variegated to occur, thereby causes printing effect inferior.
The coating process of scraping article (bar) formula is subjected to the solids content of used colored paint color and the restriction of viscosity.The colored paint that roller bar type coating process provides usually its solids content and viscosity be coated with the color of colored paint of formula than scraper plate low.Therefore, for the coating process of scraping article formula, the coating weight that is applied to paper or paperboard surface is impossible arbitrarily change.When these parameter unbalances of solids content, viscosity and coating weight of coating, will not make us desirably causing the surface quality of coated paper or cardboard to descend.And the roller rod of being denuded by colored paint is coated with the smooth of top layer for keeping, and needs periodic replacement.
Roller coat formula (film) coating process formula is the special complex method that a kind of paper feeding and cardboard provide colored paint, its operating condition scope is narrow and small, this viscosity with surface characteristics, matrix pores rate, solids coatings and the coating of matrix is relevant, and these variablees must be determined when obtaining the coating weight of each service speed and each requirement.The imbalance of these variablees can cause forming uneven film on the coated paper surface to be split, thereby causes printing quality inferior, perhaps can splash go out the little gob that is coated with when paper leaves the coating slit.If these droplets are deposited on paper surface again, can cause printing quality inferior.And, use the print roll coating method to provide the maximum coating weight of paper feeding or cardboard obviously than using scraper plate to be coated with the low of formula or scraping article formula coating process.It is obvious especially that the restriction of this coating weight seems when high-speed coating.
The common trait of above-mentioned all methods is that the surface of paper stock has irregular convex-concave surface usually, and the amount that offers the coating fluid of paper stock is to depend on that it is applied to surface nonreentrant surface or recessed.Therefore, the thickness of coating and relative ink absorption will change along with the surface of lining paper, thereby image are irregular when causing printing.Although these shortcomings are arranged, because these coating process economy particularly can have very high linear speed, these coating processes are still occupied an leading position in paper industry.
It is excessive that the common trait of described all coating techniques provides coating fluid to matrix, needs metering to remove.Under the situation of using reaction coating, this coating comprises the reactant that can react to each other, and the reaction that takes place in the metering excess coating material is useless.And for obtaining good flowability, described every kind of coating process all will be subjected to the restriction of rheology, and the rheology profile that the increase of therefore reacting additive can change coating reduces coating performance.In a lot of occasions, the chemical substance of reaction is used for giving function to coating substrate; Yet these coating will could be used by follow-up coating or step of converting, and that has just increased complexity and expense.
Curtain coating is a kind of relevant new 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 for the paper surface of moving, and use the curtain coating mode to use one deck or more colored paint layer.More particularly, prior art is such:
(i) curtain formula coating process is usually used in a colored coating is coated on the paper substrate to make the coloured coated paper of individual layer.
(ii) before using the coloured top layer of scraper plate coating process coating individual layer, curtain formula coating process is usually used in a coloured bottom is coated on the paper substrate.So, just can make multilayer colored coated paper by carrying out coloured coating continuously.
(iii) curtain formula coating process is usually used in a coloured top layer is coated on the paper substrate, and this paper substrate has been used scraper plate coating process or multiple roll coating process precoating last layer colored paint in advance.So, just can make multilayer colored coated paper by carrying out coloured coating continuously.
(iv) curtain formula coating process is usually used in two-layer special-purpose colored coating is coated on the paper substrate, so that single coating is being applied in the coating process continuously.So, just can make multilayer colored coated paper by carrying out coloured coating continuously.
Prior art as discussed above is disclosed,, so may produce with respect to the coated paper surface of using conventional coating process to have better quality the paper surface that the colored paint of individual layer is used to move with the method for curtain coating.Yet, the continuous application of the colored paint of individual layer can be subjected to the restriction of curtain coating technology medium power factor with the curtain coating technology.Especially for light paint, can only carry out under with the lower coating speed of conventional coating process, because curtain coating is unsettled under high coating speed, and this also can cause inferior coating surface.Regrettably, no matter use above-mentioned any method, because the requirement of coating position, accessory such as driver, the requirement of drier etc., and hold the needed space of machine, under continuous coating position, the individual layer colored paint is applied to paper continuously or cardboard all will drop into a large amount of capitals.
Be coated with paper and the cardboard that one deck has the coating of functional additive and be called as functional product, its coating is called as functional coating, and these functions include: impermeability, printing quality, adhesivity, release property and as color, brightness, opacity, the optical property of glossiness etc.The coating composition of giving these performances also can be referred to as functional additive.Functional product comprises all kinds of paper, as from abrasive paper, and stamp paper, wallpaper, organosilicon discharges paper, food Package paper, greaseproof paper, waterproof paper, saturated banded lining paper.
Be widely known by the people with the coating method application of coating multiple coating simultaneously, United States Patent (USP) 3508947 and 3632374 has been described photosensitive material has been applied on paper and the plastic matrix.Yet,, can only under low coating speed, use because the viscosity and the solids content of sensitization liquid and emulsion are all low.
Except being applied to photosensitive material, carry out simultaneously multi-layer coatedly also in the technology of the quick property of manufacturing power copy paper, disclosing with coating method.For example, United States Patent (USP) 4230743 has disclosed in a specific embodiment bottom and the second layer and has coated simultaneously on the mobile paper stock, and wherein bottom is made up of the microcapsules as main component, and the second layer is made up of the 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 viscosity in the time of 22 ℃ that contains developer is 10-20cps.
Japanese patent application JP-10-328613A discloses with curtain formula coating process two coatings has been coated on the paper stock simultaneously to make ink jet paper.According to its used coating composition of mentioning is the aqueous solution of solids content quite low (8% percentage by weight).In addition, need add thickener for the characteristic of the non newtonian mechanics that obtains coating solution.The embodiment of Japanese patent application JP-10-328613A has disclosed and has been only acceptable at when coating linear speed coating quality when 400m/min is following.The low running speed of coating process is not suitable for producing economical printing paper, particularly commodity printing paper.
Because conventional deficiency of producing commercial coating technique with paper, people's a kind of coating process that waits in expectation can improve the character of coating substrate, as the printing quality of the coating substrate of gained.
For the present invention, the most basic technical problem is the shortcoming that overcomes prior art, thus provide a kind of can be with the coating process of the coating that comprises one or more reactants.Another aspect of the present invention provides the coating process of the adverse effect that reacts to each other between the reactant that a kind of character of used coating can not be subjected to existing in the coating.And another object of the present invention provides coating substrate that improves performance and the method for producing this coating substrate.
Summary of the invention
The method that solves the used production coating substrate of technical problem of the present invention may further comprise the steps:
A) form a free-pouring curtain, described curtain contains at least one first component and one second component that can react to each other;
B) described curtain is contacted with a continuous matrix.
In a specific embodiment, the present invention is the method for producing a kind of coating substrate, comprises the steps:
A) form a composition, the free-pouring curtain of multilayer, described curtain comprises two-layer at least, each layer curtain have at least one first component can with at least one second component reaction of another layer;
B) described curtain is contacted with a continuous matrix.
In the preferred specific embodiment, the layer that contains first component with contain second component layer between have one deck internal layer at least.
In another embodiment, the method invention of producing coating substrate has solved problem of the present invention, and this method may further comprise the steps:
A) form a free-pouring curtain, comprise in the described curtain at least one component can with himself or with another kind of compound reaction;
B) described curtain is contacted with a continuous matrix,
At least one component in the described curtain begins reaction in the process of coating, from essence, understood complete reaction before coating process is finished.
In another embodiment, the method for producing coating substrate has solved problem of the present invention, and this method comprises:
A) form a free-pouring curtain, described curtain has at least one deck to comprise the component that can react;
B) described curtain is contacted with a continuous matrix.
Can comprise complete one first component and at least one second component lacked that can react to each other in the formation step a) in the composition of one deck at least of free-pouring curtain, perhaps can comprise a reaction system, wherein the reaction of at least one reactive component can be by with the catalyst in the component, and the method for initator or activator is induced or by being exposed to as inducing under heating or the emittance." reactive component " used herein meaning is the material that contains during the material that can react and/or initiation catalysis or other react." coating process " used herein meaning be a kind of comprise the method that be coated with a point matrix make be coated be fix and/or coating substrate finished for sale.
Preferably, the free-pouring curtain of described step a) is the compound free-pouring curtain of multilayer.
Can make curtain coating be used to react coating, preferred three kinds of main method are arranged, they are:
1) pre-coating reaction---first and second components that can react to each other just in time before coating fluid passes through or by in the curtain coating top, join in the described coating fluid, also can be by directly mixing;
2) be coated with reaction---in this step, two-layer or more conversion zone is ready to and merging in the curtain that falls, so that reaction can begin in the coating application process.
3) back coating reaction---here, at least one conversion zone is introduced in coating, and reaction is after being used for matrix with described coating but carried out before coating substrate is finished.
Therefore, preferably, in free-pouring curtain and/or when being used for matrix, and/or by as pressure, heat, the change of PH, when irradiations etc. cause, and/or be exposed under a kind of gas or the steam, under oxygen or ammonia, first and second component of step a) is carried out on the mould or the top of coating.
First component of step a) and the type that reacts to each other of second component are unrestricted, can be as, anionic-cationic reciprocation; Cross-linking reaction; Radical reaction; Step-reaction polymerization; Addition reaction; Curing reaction, as ultraviolet induction, oxygen is induced, the curing reaction of catalytic reaction or electron beam-induced; Acid-base reaction; Graft reaction; Ring-opening reaction; Precipitation reaction; Covert reaction; The reaction of flocculation/coagulation or several combinations.The compound of first and second components of reaction has as follows: polyvinyl alcohol and borax; Cationic starch and anion coating thing; Starch and dialdehyde; Epoxy-functional polymer and amine hardener; Polyisocyanate and polyol.In the preferred embodiments of the disclosure, in fact being reflected at of comprising in coating process lack under the extra power, at room temperature just can well carry out.
In the preferred specific embodiment, if described component at same one deck, the cross-linking reaction of so at least a first component and at least a second component just is not included in wherein.Preferably, method of the present invention is carried out under the electron beam irradiation not having.
In another preferred embodiment, do not comprise by in the coating component, adding the flocculation that calcium chloride solution is induced.
The reciprocation of described anionic-cationic relates to anionic compound and the reaction of cationic compound in coating fluid, and the character of described coating fluid is owing to the reciprocation of anionic-cationic has changed for this reason.Perhaps, the change of character is caused by flocculation, can make and use scraper plate, and the roller rod, the coating technique of spray gun (air knife) can not be used for matrix with described coating.
Thereby matrix optimization of the present invention is body paper or cardboard can prepare bodystock paper or cardboard.
In the preferred specific embodiment, the quick property of sensitive paper and/or power carbon paper is not included in the scope of the present invention.The meaning that term " does not comprise sensitive paper " can be interpreted as that each layer of used curtain does not comprise Ag-containing compound in enforcement of the present invention.The meaning that term " does not comprise the quick property of power carbon paper " can be interpreted as not comprising between the individual course of used curtain or the different layer combination of microencapsulation color template and developer.
According to the present invention, when the curtain coating unit that has a slip nozzle arrangement with provides the multilayer liquid coating when forming continuous multilayer curtain, each act layer just can be used simultaneously.Another kind can be selectively, and a kind of supply head of squash type is as stitching the shape mould or having several contiguous nozzles of extruding the mouth of pipe to use in enforcement of the present invention.In the preferred specific embodiment, all coating fluids by the curtain coating unit all are used for matrix.Preferably, before described curtain is applied to matrix, have only a fraction of coating fluid to be removed at the edge of the curtain that is shaped.Coating fluid by the curtain coating unit will be removed with the coating fluid that is not used in matrix.
According to a preferred embodiment of the invention, at least one act layer in the free-pouring curtain comprises at least a pigment.Preferably, make a kind ofly, have at least two coatings to comprise at least a pigment to be printed as purpose paper.Preferably, a top layer that guarantees printability is arranged.Described layer has improved surface nature, as glossiness or smoothness, and can be at random non-staining.The production of commercial printing paper, being coated with two has the coating of pigment enough concerning most purposes.
The inventor has shown by method of the present invention surprisingly, with comprising that the coating formulation of reactive component can prepare the coating substrate of modification at an easy rate, as paper and cardboard.
Used in the present invention curtain has a bottom or boundary layer and top layer at random, and/or at random one deck or more internal layer.Each layer comprises liquid, emulsion, suspension, dispersant or solution.Coating curtain of the present invention can comprise a layer at least, comprises at least 2 layers equally, at least 3 layers, and at least 4 layers, at least 5 layers, at least 6 layers or the more multi-layered specific embodiment.Layer in the curtain comprises one deck or more printable layer, one deck or more function layer, one deck or more space layer, one deck or more coating, one deck or layer and similar or any described combination of more giving response function.Space layer is with other at least two-layer separating.For example, the space layer between the layer of two components that respond is to be used for the beginning of reacting between component with postponing to.
A coating of the present invention preferably includes at least a pigment and/or adhesive, and this coating formula can be identical or different with the prescription of the paper coating of routine.The major function of a coating is to cover stromal surface, and this is known in the paper coating technology.Conventional formulation for coating material as the coating color of mentioning in industry, can use as coating layer.Useful in the method for the invention pigment comprises clay, kaolin, talcum, calcined clay, calcium carbonate, titanium dioxide, satin white, synthetic polymer pigment, zinc oxide, barium sulfate, gypsum, silica, aluminium hydroxide, mica and diatomite.Especially preferred kaolin, talcum, calcined clay, calcium carbonate, titanium dioxide, satin white, synthetic polymeric pigment comprises the polymeric pigment of hollow.
Adhesive useful in the invention process comprises, for example: styrene-butadiene latex, cinnamic acrylic ester latex, cinnamic acrylic ester-acrylonitrile latex, styrene-butadiene-acrylic ester-acrylonitrile latex, styrene-butadiene-acrylonitrile latex, styrene-maleic anhydride latex, cinnamic acrylic ester-maleic anhydride latex, polysaccharide, protein, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, epoxy resin, cellulose derivative, and polyurethanes.Preferred adhesive comprises as carboxylation of styrene-butadiene latex, carboxylation of styrene-acrylate latex, carboxylation of styrene-butadiene-acrylonitrile latex, carboxylation of styrene-maleic anhydride latex, carboxylated polysaccharides, protein, polyvinyl alcohol and carboxylation poly latex.Polysaccharide comprises: agar, and mosanom, starch comprises the modified starch as heat modification starch, carboxymethylated starch, carboxyethylation starch and oxidized starch.Used in the present invention protein example comprises albumin, soybean protein and casein.Wider adhesive scope can be the adhesive of commercial usefulness.
When using the curtain of multilayer, every layer coating weight can be regulated in the curtain, thereby obtains the desired coating substrate character of expection.Have at least one deck to expect to have in the layer of the curtain of multilayer and be less than 30g/m
2Dry-coated amount, preferably be less than 20g/m
2, more preferably 10g/m
2, more preferably 5g/m
2, 3g/m most preferably
2
Curtain of the present invention comprises a boundary layer, and this layer contacts with applied matrix.An important effect of this boundary layer is exactly the humidity that improves matrix paper.Described boundary layer has a more than function.For example, except the increase of humidity, boundary layer can cover matrix, improves function, as adhesiveness, and constancy, the combination of hardness or each function.Boundary layer can comprise that a reactive component maybe can not have reactant.When being used for the curtain of multilayer, the best relative thin of boundary layer a bit.Be used for multilayer the curtain boundary layer coating weight preferably from 0.1 to 5g/m
2, more preferably from 1 to 3g/m
2
In preferred embodiment of the present invention, boundary layer comprises one or more of following material: dispersant, as latex, comprise the latex that the swollen property of alkali expands, the mixture of starch and poly-(ethylene acrylic) copolymer, or water miscible polymer, as polyvinyl alcohol, starch, alkali solubility latex, poly(ethylene oxide), or polyacrylamide.Boundary layer can be at random painted, is preferred for some purposes.
Curtain of the present invention can comprise one deck or more function layer, and the purpose of functional layer is to give the function of wanting to coated paper.Functional layer can optionally provide, and for example, following at least is a kind of: printability; Impermeability, as damp-proof layer, anti-fragrant layer, waterproof or steam layer, antilysis layer, anti-oil reservoir, grease-proof layer; Non-oxidizability; Thin plate hardness; Antiflex cracking; The constancy of paper; Release property; Adhesiveness; Optical property, as color, brightness, opacity and smoothness etc.In a specific embodiment of the present invention, the reaction of first component and second component can be given layer function in the coating.The sizable functional coating of viscosity can not be used for conventional continuous coating process, because the coating material of viscosity has matrix is adhered to directed roller or the trend on other apparatus for coating.On the other hand, the present invention simultaneously the method for coating multiple coating allow functional coat is placed on and do not contact with the defencive function coating below the top layer with the coating machine.
The solids content of functional layer can be regulated on a large scale according to the function of wanting.The solids content of the preferred functional layer of the present invention can reach 75% of functional layer gross weight, and viscosity can reach 10,000cps (brookfield viscosity, rotating shaft 5,100rpm, 25 ℃), more preferably 50 to 3,000cps.Preferably, the coating weight of functional layer is 0.1 to 30g/m
2, more preferably 0.5 to 10g/m
2, most preferably be 1 to 3g/m
2In some cases, for example when using coloring agent or under the situation such as some reactant of borax, the coating weight of functional layer can be lower than 0.1g/m
2
A functional layer of the present invention can comprise following at least a: the ethylene, propylene acid polymer; Polyethylene; Other polyolefin; Polyurethane; Epoxy resin; Polyester; Adhesive, as styrene butadiene latices, styrene-acrylate latex, carboxylated latex, starch, protein or similar; Setting agent, as starch, styrene acrylic copolymer, styrene maleic anhydride, polyvinyl alcohol, polyvinyl acetate, carboxymethyl cellulose or analog; The barrier layer, as silicones, wax or analog.
Each functional layer can comprise, but and unrestricted at least a pigment and/or adhesive that is used for coating as previously described and/or the reactant of one or more of comprising.
If want, for example can contain at least a additive in Mu one deck at least, at least a dispersant, at least a lubricant, at least a water retention agent, at least a surfactant, at least a Optical Bleaching Agent, the dyestuff of at least a color or colouring agent, at least a thickener, at least a defoamer, at least a antifoaming agent, at least a antimicrobial, at least a water-soluble pigment or colouring agent also comprise described these combination or analog.Poly(ethylene oxide) is a kind of preferred additives, can be used for any one deck.In the preferred specific embodiment, oxirane is used as thickener, preferably at least in internal layer.Advantageously, the mean molecule quantity of oxirane has 50,000 at least, preferably has 100,000 at least, and more preferably at least 500,000, most preferably at least 800,000.Preferably, the amount of used oxirane will enough prevent cratering, preferably less than 2% of the percentage by weight of used solid matter in the layer.
To achieve the object of the present invention, in the multilayer curtain, being referred to as from matrix paper layer farthest is top layer.This layer is the layer that will print in the above, though coated paper of the present invention conventional method such as roller bar, scraper plate, roller coat, scraping article or air knife (spray is robbed) coating technique and similar approach are coated with also again and can produce.Top layer can be a coating layer or a functional layer, comprises gloss layer, can comprise a reactant.In a preferred embodiment of the invention, top layer is quite thin, for example, coating weight from 0.5 to 3g/m
2Advantage is that this method allows to use relatively cheap material under top layer, but the paper of producing still has good printing.In a specific embodiment, top layer is not contain inorganic pigment.
According to a significant preferred embodiment, top layer has a kind of luminous preparation.The novel combination of luminous preparation and simultaneous multilayer curtain coating make the good curtain coating of glossiness have advantage.
Useful in the present invention luminous preparation comprises the gloss additive, and for example, by polymerization such as styrene, the synthetic polymer pigment of the polymerisation of acrylonitrile and/or acrylic monomers preparation comprises polymer pigment hollow or solid.The glass transformation temperature of synthetic polymer pigment optimization is 40-200 ℃, and more preferably 50-130 ℃, preferred particle size is 0.02-10 μ m, more preferably 0.05-2 μ m.The content of luminous preparation is the 5-100% percentage by weight of solid granulates in the gloss additive, more preferably 60-100% percentage by weight.The glossiness varnish of luminous preparation of another kind of type, as those based on epoxy acrylate, polyester, acrylic polyester, polyurethane, polyacrylic acid ether, oleoresin, nitrocellulose, polyamide, the various forms of ethylene copolymer and polyacrylate.According to a preferred embodiment of the invention, the viscosity of top layer is greater than 20cps (25 ℃ the time).Preferred range of viscosities is 90cps to 2, and 000cps is preferred from 200cps to 1,000cps.
When curtain had 3 layers at least, it had an internal layer at least.If a stable curtain can remain, the viscosity of internal layer and particulate solid content are not critical.Internal layer is functional layer or coating layer preferably.In the time of a more than internal layer, functional layer and coating layer can be used in combination.For example, internal layer can be the combination of identical or different functional layer, the combination of identical or different coating layer, or the combination of functional layer and coating layer.Internal layer also may comprise reactant.
Method of the present invention has been expanded the limitation in the paper coating technique, has given the unprecedented flexibility of papermaker and has prepared the ability of new coated paper.
Free-pouring curtain has a preferred solids content of expection, is 10% percentage by weight at least, preferred 40% percentage by weight, more preferably 45% percentage by weight, most preferably 50% percentage by weight.Advantageously, the solids content of free-pouring curtain can from 10% to 80%.The content of the preferred particulate solid of one deck at least of the free-pouring curtain of a multilayer of the present invention is wanted 40% percentage by weight at least, preferably at least 50% percentage by weight, more preferably at least 65% percentage by weight.
The special advantage of a specific embodiment of the present invention is with at least two coatings of curtain coating method continuous application even can to obtain quite thin layer or rephrase the statement under high speed be very low coating weight.For example, every layer coating weight can be from 0.01 to 10g/m in synthetic curtain
2, more preferably 0.1 arrive 3g/m
2Every layer coating weight can be with other layers identical, perhaps can and other layers between be very different; Therefore a lot of combinations all is possible.
Method of the present invention can production coating weight wide range matrix.Be coated on the paper coating weight preferably from 3 to 60g/m
2, more preferably from 5 to 25g/m
2The coating weight of doing of the coating expection of preparing in curtain is to be less than 60g/m
2, also can select to be less than 30g/m
2, also can select to be less than 20g/m
2, also can select to be less than 15g/m
2, also can select to be less than 12g/m
2, also
CanSelection is less than 10g/m
2, most preferably be less than 5g/m
2
In a specific embodiment of the present invention, the coating weight of top layer ratio is low with the coating weight of the layer of basic paper or substrate contacts.The coating weight of top layer preferably be less than with basic paper or substrate contacts the layer coating weight 70%, more preferably less than 50%.Therefore the raw material availability that is reached in the coating operation of paper or cardboard has just improved greatly.In another embodiment, the coating weight of top layer is than the coating weight height of the layer below it.Coating process unlike routine, the multi-layer coating method that the present invention carries out simultaneously allows with a large amount of inexpensive relatively raw material, for example, be lower than with your raw material make top layer as thin as a wafer or with the combining of expensive reactant such as curing agent, the quality of the coated product of finishing does not so reduce.In addition, method of the present invention allows the paper that preparation was never produced in the past.For example, in curtain, can include the internal layer of sticky feature.
No matter use which specific embodiment, a significant advantage of the present invention is that method of the present invention can be carried out under very high coating speed, and this speed can only be coated with scraper plate up to now, and the scraping article coating could obtain under the method for roller coat.Common linear speed is at least 300 meter per seconds among the present invention, preferred at least 400 meter per seconds, and more preferably 500 meter per seconds, in the scope of 600-3200 meter per second, more preferably at least 800 meter per seconds are in the scope of 800-2500.Speed at least 1000 meter per seconds that linear speed or matrix move in a specific embodiment of the present invention, preferably at least 1500 meter per seconds.
Preferably, the continuous reticulate pattern matrix of step b) is neither pre-coating press polish in advance.In another embodiment, the continuous net matrix of step b) is not pre-coating, and in another embodiment, the continuous net matrix of step b) is not pre-press polish.It is 20-400g/m that the continuous net matrix of step b) has a preferred grammes per square metre or basic weight
2
Description of drawings
Fig. 1 is a cutaway view of explaining curtain coating unit 1, and a slip nozzle row 2 is arranged, and is used for carrying a fluid stream 3 of curtain layer to form a continuous multilayer curtain 4.When reaching the dynamic equilibrium state, the curtain laminar flow amount that flows into slip nozzle row 2 is a complete equipilibrium with the flow that flows to exclusive of slip nozzle.The multilayer curtain 4 of free-falling contacts with paper stock 5, and it carries out continuously, and paper stock 5 can be used multilayer curtain coating cloth like this.The influence that the air of the paper stock 5 by will following high-speed mobile with a roller 6 flows is reduced to minimum method changes the direction of motion of paper stock 5 rapidly before dispensing area.
Concerning prior art the superiority of the inventive method be can by to matrix with a curtain that comprises at least two reactive components, thereby obtain to have specific characteristics can coated paper. Described method allows anyone to prepare to have the special nature coating substrate, and this is to be given by the reaction of reactant described in the special layers. Method known to from prior art is used excessive coating color, but these methods can not be used for matrix with the coating that contains reactant. And described coating substrate is applicable to any printing process printing known to the workman that is skilled in technique.
The specific embodiment
With embodiment the present invention is described below.Unless special explanation is arranged, all percentage all is percetage by weight.
Embodiment:
Following material is used for constituting the layer in the applying structure of reaction:
Ameo:3-aminopropyl-triethoxysilane (DYNASYLAN AMEO comes from AG, Hanau, Germany).
Carbonate (A): the granular size in the water has the divided calcium carbonate prose style free from parallelism (HYDROCARB 90 ME come from Plauess-Srauffer) of 90%＜2 μ m, solids content 77%.
Carbonate (B): the granular size in the water has the divided calcium carbonate prose style free from parallelism (HYDROCARB 60 ME come from Plauess-Srauffer, Oftringen, Switzerland) of 60%＜2 μ m, solids content 77%.
Catalyst: combine (the coming from Air Products, Allentown, PA, the U.S.) of organotin and dibutyl tin dilaurate.
Clay: the granular size in the water has No. 1 kaolinton dispersion (HYDRAGLOSS 90, come from JM Huber Corp.Have de Grace, Maryland, the U.S.) of 98%＜2 μ m, solids content 71%.
The epoxy material material: be equivalent to the dispersion of bisphenol-A of the epoxy resin of 500 epoxy radicals based on solid weight, the solids content in the water is 55%.
DSP: the solids content in the dispersion of ethylene acrylic acid co polymer (DSP70 the comes from The Dow ChemicalCompany) water is 15%.
Glyeo:3-glycidyl propoxyl group-triethoxysilane (DYNASILAN GLYEO comes from Degussa AG, Hanau, Germany).
Glyoxal: polyhydroxylated two urea formaldehydes of reaction (Cartabound GH Liquid comes from Clariant AG Lorrach Germany).
Curing agent: amino epoxy hardener (XZ 92441.01 comes from The Dow ChemicalCompany).Solids content 75% in the water
Isocyanates: hexamethylene-1, the aliphatic polyisocyanic acid salt of 6-diisocyanate (Bayhydur VPLS 2319 comes from BayerAG, Leverkusen, Germany).
Latex (A): solids content is 50% in this ethene of carboxylation butadiene latex (DL 966 comes from The Dow ChemicalCompany) water.
Latex (B): solids content is 50% in this ethene of carboxylation butadiene latex (DL 980 comes from The Dow ChemicalCompany) water.
Latex (C): solids content is 27% in the carboxylation acrylate latex of alkali swelling (XZ 92338 the comes from The DowChemical Company) water.
Latex (D): solids content is 51% in carboxylation acrylate latex (XU31215.5 the comes from The Dow ChemicalCompany) water.
Latex (E): solids content is 50.5% in carboxylation acrylate latex (UCAR Latex DT 211 the comes from The DowChemical Company) water.
Latex (F): solids content is 50% in this ethene of carboxylation butadiene latex (DL 939 comes from The Dow ChemicalCompany) water.
Poly(ethylene oxide): molecular weight is 300 poly(ethylene oxide) (PEG 300 comes from Fluka).
PVOH: solubility is 15% low-molecular-weight synthesizing polyethylene alcohol (MOWIOL 6/98, comes from Clariant AG, Basel, Switzerland).
Surfactant (A): water miscible two-salts of alkyl sulfosuccinates sodium (AEROSOL OT comes from Cyanamid, Wayne, the New Jersey U.S.), the solids content in the water is 75%.
Surfactant (B): the water miscible Exxal 12 ethoxylate of TERGITOL TMN6 6EO (coming from TheDow ChemicalCompany), the solids content in the water is 90%.
Thickener: molecular weight is 900,000 deionized water dissolubility polymer (oxirane) (POLYOXWSR-1105 comes from DowChemicalCompany), and the solids content in the water is 4%.
Brightening agent: diamines-1, the fluorescent whitening agent that the 2-stilbene disulfonic acid is derived (TINOPALABP/Z comes from Ciba Specialty Chemicals Inc. Ba Saier, Switzerland).
Borax: sodium tetraborate, net content are＞98%, obtain from FLUKA.
Starch (A): cationic starch (C Size SP5885 comes from Cerestar, Krefeld, Germany).
Starch (B): anionic starch (CFilm0311 comes from Cerestar, Krefeld, Germany).
Coating process
By the quantity that following form provides mentioned component is mixed, point out unless have in addition, all here composition weight all is to use dry weight.The pH value of colored paint preparation can be regulated by adding NaOH solution (10%), and is as shown in table 1.Can add suitable quantity of water and regulate the solids content of preparation.According to following wherein a kind of method preparation is applied on the paper.
Coating process 1: used curtain formula coating machine is the multilayer sliding mould tool curtain formula coating machine of producing with Troller SchweizerEngineering (TSE, Murgenthal, Switzerland).Curtain coating equipment is equipped with the lubricated edge guide plate of thin current, and the bottom of edge guide plate be exactly the coated paper edge directly over a vacuum suction device of removing the lubricated water in edge is housed.For obtaining the coating weight of expection, measure the precise volumes of mould with the pump of surveying volume.In addition, curtain formula coating machine be equipped with a vacuum suction device with remove in paper substrate from the sail against the current air of interface surface of curtain impact zone.The height of curtain is 300mm.Coating formulation will outgas before being used for removing bubble in advance.After being coated with on the paper stock, paper will be used the hot-air drier drying.
Coating process 2:Except following difference, this method is the same with method 1.Use the multilayer sliding mould tool curtain formula coating machine of producing by Leuthold AG that preparation is applied on the paper.When in the preparation volatile component being arranged, under having condition of stirring, preparation not poured in the material container at least 12 hours before use, so generation is the nature degassing.When two kinds of coating formulations need react before the input sliding mould, they will be pumped in the little airtight container, stir with scull under the speed of 600rpm.
Assay method
Brookfield viscosity
With Bu Shi RVT type viscometer determining viscosity.(Bu Shi engineering experiment chamber, Stoughton Massachusetts, the U.S.).The sample of 600ml is put into the beaker of 1000ml,, measure viscosity under the 100rpm spindle speed at 25 ℃.
Sheet gloss
The gloss of paper is measured under 75 ° of incidence angles with Zehntner ZLR-1050 device.
The ink degree
Adopt and measure with Lorrilleux8588 chilli oil China ink with Pruefbau Test Printing element.0.8g/m
2(or difference 1.6g/m
2) quantity of ink be used to measure the calibration tape of coated paper, used calibration tape is to be installed on the platen that the long back side is rubber with a steel seal brush disk.Used ink pressure is 1,000N, and speed is 1m/s.Printer belt will be at 20 ℃, and drying is 12 hours under 55% the minimum indoor humidity.Just under 75 ° of incidence angles, measure glossiness then with Zehntner ZLR-1050 instrument.
The ink solidification degree
Measure with Pruefbau TestPrinting element.Per minute distributes the printing ink (Huber520068) of 250mm3 on distributor.An operplate printing disk just is coated with by printing ink and has dyed 15 second on distributor.This disk is placed on first print position.Be not coated with the operplate printing disk that dyes on second print position, having placed one under the pressure of 400N by printing ink.Describedly be installed in coating paper tape on the platen that the back side is rubber, be printed under the speed of 1.5m/s at the squeegee pressure of 1000N.When printing takes place when not required between.When being with after primary importance prints, will move on to second printing position to band by moving handle, perhaps cry the set-off position.In the set-off position, between paper that has printed and disk, put a plain pape.15,30, in the time of 60 and 120 seconds, moving handle is pressed plain pape to the opposite direction of printing pattern in the set-off position.Transfer to the amount of the mobile printing ink on the plain pape from the paper that has printed and measure, resemble the mensuration of optical density (OD) by the ink density device.
Brightness
Brightness is measured with Zeiss Elrepho2000.Brightness is measured on a pile scraps of paper according to iso standard 2496.The result provides as R457.
Opacity
Opacity is to measure with Zeiss Elrepho2000.Opacity is to measure mensuration (R on (R0) and a pile scraps of paper on the monolithic of backing black standard
∞).The result is with R0/R
∞* 100 (percentage by weight) form provides.
After-flame is measured
This test is to be used for explaining that coating is without the distribution and the uniformity (except the sample of full coat) on printing and the paper that printed.
Step:
1. the paper of 4 * 4cm was immersed in the aqueous solution of NH4Cl of 10% (w/w) 1 minute.
In baking box with 120 degrees centigrade of dry test papers 3 minutes.
3. paper being moved on to 5-10cm place, electric furnace top burns until there not being cigarette (sample can not burn).
4. mensuration brightness.Therefore this step is to be coated with to dye black coated fiber, and higher brightness value coating of having shown applied improvement is brighter than the fiber of blackening.
Intersection angle
Intersection angle is measured with Fibo 1100 dynamic absorptiometers (Fibo system AB Sweden) with the TAPPIT-558 method.
Resist drying adheres to (IGT)
This thermometrically paper surface does not have the ability of accepting ink transfer under the situation of adhesion.This test is carried out on A2 type printability tester, commercial can carrying out at IGT Reprotest BV.Coating paper batten (4 millimeters * 22 millimeters) is 36 Newtonian times with the aluminium dish printings of coating printing ink at squeegee pressure, with pendulum drive system and the high viscosity test oil (redness) led from Reprotest BV tester.After being completed for printing, coating layer begins to show that the distance of adhesion marks under stereoscope.The distance of border note changes into the IGT rate curve then, is that the speed of unit is read from the respective drive curve with the cel.Two-forty is represented the high resistance to the drying adhesion.
The paper roughness
The roughness of coating paper surface is measured with Parker printed matter surface roughness tester.The sample thin layer of coating paper pressing plate extruding force with 1000 kPas between a polyester film cork sheet and a measurement end clamps.Compressed Gas pours into measuring instrument and reaches 400 kPas, measures in the leakage of measuring air between end and the coating paper surface.The roughness of higher numeric representation coating paper surface is higher.
Paper hardness
Paper hardness Kodak hardness method, TAPPI535-PM-79 or Gurely hardness method, TAPPI543 measures.
Coating weight
The coating weight that obtains in each coating experiment is obtained by following data computation, coating is transported to act known volume flow rate of the pump at formula coating top, the speed of the paper that below curtain formula coating top, constantly moves, the density of coating curtain and the weight percent content of solid content, and the width of coating curtain.
Water proofing property
The performance of breaking takes place to be coated with and measures with the anti-resistance of the moistening friction of Adams determination method in the coated paper after preventing to absorb water.(24 * 2.5cm) are fixed on the bronze wheel of a constant speed rotation, load a rubber rollers then on paper tape, and this roller soaked in the plate of distilled water is housed 45 or 60 seconds with paper tape.If coating is broken, rotation can make the water muddiness in the plate.After rotating end, the light transmission of the water in the disk is fixed with mixing the degree instrumentation.Low transmisivity data has shown has serious coating to break.
Control experiment A and embodiment 1 to 4
These embodiment utilize borax in one deck and the reaction between the PVOH in another layer.Reaction increases the formation degree of viscosity and gelinite fast.In table 1, done detailed explanation.
Table 1
With coating process 1. coating being coated onto wear intensity with the speed of 1000m/min is 4.3 microns containing on the wood pulp based paper.The two kinds of coating situations that have that are used for embodiment 1,2 and 3: the coating weight of coating situation 1-bottom is 1g/m
2, the top layer coating weight is 7g/m
2, the coating weight of coating situation 2-bottom is 2g/m
2, the top layer coating weight is 6g/m
2These two kinds of coating situations have been tested the influence that increase brought of the amount of reaction bottom.What check experiment was used is two kinds of identical coating situations, but reacted constituent (borax) has been omitted.Embodiment 4 usefulness one three layers coating, borax is contained in thin intermediate layer.For embodiment 4, the coating weight of bottom is fixed as 1g/m
2, the coating weight of top layer is 7g/m
2, and the coating weight in middle level is at 0.018g/m
2(coating situation 1) is to 0.036g/m
2Change between (coating situation 2).The character of the coated paper of these embodiment is listed in table 2 and the table 3.
Table 2
| Contrast A | Embodiment 1 | Embodiment 2 | |
Embodiment 4 | |
| Coated paper character | Coating situation 1 | Coating situation 1 | Coating situation 1 | Coating situation 1 | Coating situation 1 |
| 75 ° of paper glossiness (percentage) | 43 | 43 | 45 | 43 | 37 |
| 75 ° of ink degree; 0.8g/m 2Printing ink (percentage) | 58 | 62 | 62 | 58 | 51 |
| 75 ° of ink degree; 1.6g/m 2Printing ink (percentage) | 65 | 69 | 68 | 71 | 63 |
| Roughness PPS (μ) | 1.8 | 1.7 | 1.7 | 1.6 | 1.8 |
| ISO brightness R457 (percentage) | 76.8 | 78.4 | 77.1 | 77.2 | 78.4 |
| Opacity (percentage) | 92.8 | 92.8 | 93.5 | 93.6 | 93.8 |
| Set-off degree (density) after 15 seconds | 0.08 | 0.11 | 0.11 | 0.05 | 0.09 |
| Set-off degree (density) after 30 seconds | 0.00 | 0.00 | 0.01 | 0.00 | 0.00 |
| Set-off degree (density) after 60 seconds | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Set-off degree (density) after 120 seconds | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Burn-off rate is measured brightness | 28.4 | 30.8 | 28.9 | 31.3 | 30.5 |
| Bending hardness machine direction (mNm) | 0.050 | 0.049 | 0.055 | 0.056 | 0.060 |
Table 3
| Contrast A | Embodiment 1 | Embodiment 2 | |
Embodiment 4 | |
| Coated paper character | Coating situation 2 | Coating situation 2 | Coating situation 2 | Coating situation 2 | Coating situation 2 |
| 75 ° of paper glossiness (percentage) | 37 | 39 | 41 | 41 | 32 |
| 75 ° of ink degree; 0.8g/m 2Printing ink (percentage) | 52 | 58 | 56 | 54 | 47 |
| 75 ° of ink degree; 1.6g/m 2Printing ink (percentage) | 63 | 69 | 70 | 62 | 60 |
| Roughness PPS (μ) | 2.0 | 1.8 | 1.7 | 1.4 | 1.9 |
| ISO brightness R457 (percentage) | 77.0 | 77.8 | 76.6 | 77.3 | 78.3 |
| Opacity (percentage) | 92.6 | 93.3 | 92.9 | 92.3 | 93.7 |
| Set-off degree (density) after 15 seconds | 0.06 | 0.12 | 0.19 | 0.24 | 0.22 |
| Set-off degree (density) after 30 seconds | 0.01 | 0.01 | 0.00 | 0.01 | 0.05 |
| Set-off degree (density) after 60 seconds | 0.00 | 0.00 | 0.00 | 0.00 | 0.01 |
| Set-off degree (density) after 120 seconds | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| The mensuration that burnouts brightness | 27.4 | 27.9 | 29.5 | 29.9 | 29.4 |
| Bending hardness machine direction (mNm) | 0.049 | 0.057 | 0.057 | 0.064 | 0.057 |
The result has shown that the glossiness of the reaction pair paper between borax and the PVOH and the influence of roughness all are faint, to the ink degree, opacity, hardness, coating scope with after-flame experiment decision all has very significant raising, to the influence of ink solidification degree slowly, the brightness that the thickness by the boracic layer of sand is determined makes some difference.Relatively be coated with state 1 and coating state 2, find the amount of borax is doubled and can have a significant impact ink solidification degree and hardness.
Check experiment B and embodiment 5
This embodiment is used in the reaction of cationic starch with the anion paper coating top layer of routine of bottom.Check experiment has replaced cationic starch with conventional anion coating starch.In table 4, this has been done detailed explanation.
Table 4
With coating process 1. coating being coated onto wear intensity with the speed of 1000m/min is 6.2 microns containing on the wood pulp based paper.The coating weight of bottom is 0.5g/m
2, the coating weight of top layer is 6.5g/m
2The character of this coated paper is listed in the table 5.
Table 5
| Coated paper character | Contrast B | Embodiment 5 |
| 75 ° of paper glossiness (percentage) | 35 | 37 |
| 75 ° of ink degree; 0.8g/m 2Printing ink (percentage) | 47 | 52 |
| 75 ° of ink degree; 1.6g/m 2Printing ink (percentage) | 58 | 68 |
| The dry adhesive capacity (cm/s) of IGT | 52 | 57 |
| Set-off degree (density) after 15 seconds | 0.48 | 0.57 |
| Set-off degree (density) after 30 seconds | 0.20 | 0.25 |
| Set-off degree (density) after 60 seconds | 0.07 | 0.09 |
| Set-off degree (density) after 120 seconds | 0.04 | 0.01 |
| Bending hardness machine direction (mNm) | 0.042 | 0.050 |
Measure by the dry adhesive organ of IGT, the use of cationic starch all improves a lot to hardness and coating strength.In addition, the ink solidification degree has reduced.
Embodiment 6
This embodiment illustrated amyloid preparation and can and the dialdehyde solution (glyoxal) of starch reaction between interfacial reaction.Allocated starch in the bottom into, the middle level is a glyoxal solution.In the preparation glyoxal total consumption be 15% of amount of starch.The top layer of coating is the color-printed layer of a routine.Do not contain glyoxal and amyloid double-deck the coating in contrast.Coating formulation such as table 6 describe in detail.
Table 6
With coating process 2. speed of coating with 700m/min is coated onto on the basic paper that contains wood pulp, coating weight is as shown in table 6.That handles through press polish has all measured the dry adhesive capacity of anti-IGT with uncalendered coated paper.The result is as shown in table 7.
Table 7
| Uncalendered | IGT(cm/s) |
| Reference | 95 |
| Contain glyoxal | 108 |
| Handle through press polish | |
| Reference | 62 |
| Contain glyoxal | 76 |
Measure as the dry adhesive organ of IGT, the use of the starch of reaction/glyoxal system has improved coating strength.
Measure the hardness and the water proofing property of opening respectively with Gurley hardness method (intersecting machine direction) and the moistening friction method of Adams through calendered paper.
Table 8
| Sample | Gurley hardness (Gurley unit) | Moistening friction result (percent transmittance) |
| Reference | 375.5 | 4.7 |
| Contain glyoxal | 397.8 | 83.5 |
Contain glyoxal sample shown the increase of hardness and fabulous water proofing property.
Embodiment 7
This embodiment has illustrated the performance of improving coated paper with quick-setting latex.Fast the initator of curing reaction be considered to polymer with nitrogen from neutrality to being full of cationic conversion, the volatilization of ammonia changes PH exactly when coating and/or dry paper because in the preparation.In table 9, this has been done detailed explanation.
Table 9
With coating process 2. speed of the coating of three-decker with 1000m/min will be arranged, coating weight as shown in table 9 is coated onto and does not contain on the wood pulp based paper, and basic coating weight is 120g/m
2Top layer contains reaction system.In reference examples, do not contain polymer with nitrogen.The intersection angle that the paper of quick cure system is arranged is 74 °, and contrast paper is 64 °.Fast cure polymer obviously is for paper is connected with the hydrophobic that waterproof more forms.
Embodiment 8
This embodiment has illustrated the coating that the Ethoxysilane (Glyeo) with amino-Ethoxysilane (Ameo) and glycidyl functional group carries out.Multiple reaction can appear.Except the reaction of amino group and glycidyl group, when being high enough to the hydrolysis Ethoxysilane, passes through pH the reaction of glycidyl functional group's Ethoxysilane self, and the hydrolyzing reaction takes place to be connected to form siloxanes.The method of three kinds of coated papers is proved to be.First kind of Glyeo id reaction that has been illustrated except id reaction, also illustrated simultaneously the reaction between the Ameo and Glyeo in hierarchy.The 3rd, use a kind of embedded method, the mixture of Ameo and Glyeo is used in the individual layer slit of mould.Detailed explanation is as shown in table 10.
Table 10
With coating process 2. coating is used and to be contained on the ground wood pulp base paper.Coating weight and speed are as shown in table 10.As shown in table 11 with the glossiness without the paper of press polish through the paper of press polish, table 11 has also comprised the comparative result of ink degree.Shown in reaction system under, the glossiness of paper reduces.The ink degree has significantly improved.Raising maximum through the paper of press polish.For two kinds of printing ink useful loads, the sample of reaction has shown the raising of ink and scraps of paper gloss increment.
Table 11
| Sample | Contrast | Glye o | Glyeo Ameo multilayer | The embedded mixing of Glyeo Ameo | Contrast | Glyeo | Glyeo Ameo multilayer | The embedded mixing of Glyeo Ameo |
| Whether through press polish | Not | Not | Not | Not | Be | Be | Be | Be |
| 75 ° of sheet gloss | 30 | 24 | 25 | 27 | 75 | 69 | 67 | 69 |
| 1.6g/m 275 ° of the ink degree that loads | 52 | 54 | 52 | 53 | 75 | 85 | 84 | 84 |
| 0.8g/m 275 ° of the ink degree that loads | 46 | 46 | 47 | 47 | 72 | 80 | 77 | 82 |
Without press polish and all measured through the Adams wet rub of the sample paper surface of press polish.The turbidity measurement result of twice friction is as shown in table 12, and table 12 has also shown the measurement result of intersection angle simultaneously.The result has shown that the water proofing property of coated paper has increased than nonreactive contrast.
Table 12
The water proofing property that adds the paper of Ameo reaction system coating with Glyeo and Glyeo has increased.When two kinds of response functions all exist, the intersection angle maximum.
Embodiment 9
Present embodiment has illustrated amino epoxy hardener and the reaction between the epoxides.What present embodiment was used is embedded method, and the mixture of curing agent and epoxides is added in the individual layer slit of mould.The sample of contrast does not comprise curing agent and epoxides.In table 13, done detailed description.
Table 13
With coating process 2. preparation is used and to be contained on the wood pulp based paper, coating speed and coating weight are as shown in table 13.After drying on the machine, sample will further be handled with paper, react 15 minutes to finish its reaction under 120 ℃ temperature.Measure intersection angle and paper hardness.The result is as shown in table 14.
Table 14
| Contrast | Epoxides/curing agent | |
| Intersection angle (degree) | 60.5 | 78.2 |
| Paper hardness (mNm) | 0.778 | 0.993 |
Because the reaction of epoxides/curing agent, the water proofing property and the hardness of coated paper have all increased.
Embodiment 10
Present embodiment has illustrated that being reflected at of isocyanates and polyol forms layer of polyurethane in the sandwich construction.Before being added in the mould of coating machine, present embodiment mixes with the chemicals of embedded method with reaction.In table 15, done detailed explanation.
Table 15
With coating process 2. coating is used and to be contained on the ground wood pulp base paper.The character of gained paper is shown in table 16.
Table 16
| Reaction | Contrast | |
| The lubricated friction of Adams (percent transmittance) | 99.3 | 32.8 |
| Resist drying adhesive capacity (cm/s) | Do not have and adhere to | 46 |
| Uncalendered gloss | 45 | 28 |
| Degree |
The paper that contains polyurethanes has shown good resist drying adhesive capacity and excellent waterproofness.Polyurethanes has also improved uncalendered glossiness.
Claims (86)
1. a method of making coating substrate comprises the following steps:
A) form a free-pouring curtain, described curtain comprises first component and second component that can react to each other;
B) described curtain is contacted with a continuous matrix,
Wherein, it is two-layer that described curtain comprises at least, and wherein the viscosity of top layer in the time of 25 ℃ is 90 to 2000cps.
2. method according to claim 1 is characterized in that described method comprises the following steps:
A) form a kind of composite, the free-pouring curtain of multilayer, described curtain wherein one deck comprise can with first component of second component reaction of another layer;
B) described curtain is contacted with a continuous matrix.
3. method according to claim 2 is characterized in that, in the free-pouring curtain of the multilayer of described step a) the layer that contains first component with contain second component layer between have an intermediate layer at least.
4. according to any described method in claim 2 and 3, it is characterized in that first component that can react to each other in the step a) and the reaction type of second component are selected from: the anionic-cationic reciprocation, cross-linking reaction, radical reaction, step-reaction polymerization, addition reaction, the ultraviolet induction curing reaction, electron beam-induced curing reaction, acid-base reaction, flocculation or coagulation reaction and combination thereof.
5. method according to claim 1 may further comprise the steps:
A) form a free-pouring curtain, have at least one deck to contain first component or second component in the described curtain, and
B) described curtain is contacted with a continuous matrix.
6. method according to claim 1 may further comprise the steps:
A) form a free-pouring curtain, first component and second component that described curtain has at least one deck to comprise to react to each other, and
B) described curtain is contacted with a continuous matrix.
7. according to claim 5 or 6 described methods, it is characterized in that at least a first component that can react to each other in the step a) and the reaction type of at least a second component are selected from: the anionic-cationic reciprocation, radical reaction, step-reaction polymerization, addition reaction, ultraviolet induction curing reaction, electron beam-induced curing reaction, acid-base reaction, flocculation or coagulation reaction and combination thereof.
8. according to claim 5 or 6 described methods, it is characterized in that free-pouring curtain described in the step a) be one compound, the free-pouring curtain of multilayer.
9. according to any described method among the claim 1-3, it is characterized in that first component and being reflected in the free-pouring curtain and/or when it is applied to matrix and/or when causing by heating, pressurization, irradiation and/or oxygen of second component in the step a) taken place.
10. according to any described method among the claim 1-3, it is characterized in that first component in the step a) is a polyvinyl alcohol, second component is a borax.
11. any described method according among the claim 1-3 is characterized in that first component in the step a) is a cationic starch, second component is the anion coating composition.
12., it is characterized in that comprising the top layer that guarantees printing quality in the free-pouring curtain in the step a) according to any described method among the claim 1-3.
13. according to any described method among the claim 1-3, the grammes per square metre that it is characterized in that matrix continuous in the step b) from 20 to 400g/m
2
14., it is characterized in that having at least in the multilayer curtain in the step a) the dry-coated amount of one deck to be less than 30g/m according to claim 2 or 3 described methods
2
15., it is characterized in that having at least in the multilayer curtain in the step a) the dry-coated amount of one deck to be less than 20g/m according to claim 2 or 3 described methods
2
16., it is characterized in that having at least in the multilayer curtain in the step a) the dry-coated amount of one deck to be less than 10g/m according to claim 2 or 3 described methods
2
17., it is characterized in that the dry-coated amount of the multilayer curtain in the step a) is less than 60g/m according to claim 2 or 3 described methods
2
18., it is characterized in that the multilayer curtain in the step a) haves three layers at least according to claim 2 or 3 described methods.
19., it is characterized in that the multilayer curtain in the step a) has 4 layers at least according to claim 2 or 3 described methods.
20., it is characterized in that the multilayer curtain in the step a) is of five storeys at least according to claim 2 or 3 described methods.
21., it is characterized in that the multilayer curtain in the step a) has 6 layers at least according to claim 2 or 3 described methods.
22., it is characterized in that including in the multilayer curtain in the step a) one deck at least of at least a pigment according to claim 2 or 3 described methods.
23. method according to claim 22 is characterized in that described pigment is selected from: clay, kaolin, talcum, calcined clay, calcium carbonate, titanium dioxide, satin white, synthetic polymer pigment, zinc oxide, barium sulfate, gypsum, silica, aluminium hydroxide, mica and diatomite.
24., it is characterized in that having at least one deck to contain adhesive in the free-pouring curtain of multilayer in the step a) according to claim 2 or 3 described methods.
25. method according to claim 24, it is characterized in that described adhesive is selected from: styrene-butadiene latex, cinnamic acrylic ester latex, cinnamic acrylic ester-acrylonitrile latex, styrene-butadiene-acrylic ester-acrylonitrile latex, styrene-butadiene-acrylonitrile latex, styrene-maleic anhydride latex, cinnamic acrylic ester-maleic anhydride latex, polysaccharide, protein, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, cellulose derivative and their mixture.
26., it is characterized in that having at least one deck to contain at least a Optical Bleaching Agent in the free-pouring curtain of multilayer in the step a) according to claim 2 or 3 described methods.
27., it is characterized in that having at least one deck to contain at least a surfactant in the free-pouring curtain of multilayer in the step a) according to claim 2 or 3 described methods.
28., it is characterized in that having the solid matter content of one deck at least in the free-pouring curtain of multilayer in the step a) is 40wt% at least according to claim 2 or 3 described methods.
29., it is characterized in that having the solid matter content of one deck at least in the free-pouring curtain of multilayer in the step a) is 50wt% at least according to claim 2 or 3 described methods.
30., it is characterized in that having the solid matter content of one deck at least in the free-pouring curtain of multilayer in the step a) is 65wt% at least according to claim 2 or 3 described methods.
31., it is characterized in that the solid matter content in the free-pouring curtain of multilayer in the step a) is 10wt% at least according to claim 2 or 3 described methods.
32., it is characterized in that the solid matter content in the free-pouring curtain of multilayer in the step a) is 40wt% at least according to claim 2 or 3 described methods.
33., it is characterized in that the solid matter content in the free-pouring curtain of multilayer in the step a) is 45wt% at least according to claim 2 or 3 described methods.
34., it is characterized in that matrix continuous in the step b) is basic paper or cardboard according to any described method among the claim 1-3.
35., it is characterized in that the neither also not pre-press polish of pre-coating of matrix continuous in the step b) according to any described method among the claim 1-3.
36. according to any described method among the claim 1-3, the speed that it is characterized in that matrix continuous in the step b) is 300m/min at least.
37. according to any described method among the claim 1-3, the speed that it is characterized in that matrix continuous in the step b) is 400m/min at least.
38. according to any described method among the claim 1-3, the speed that it is characterized in that matrix continuous in the step b) is 500m/min at least.
39. one kind by any coating substrate that described method makes among the claim 1-3.
40., it is characterized in that coating substrate is coated paper or cardboard according to the described coating substrate of claim 39.
41. a method of producing coating substrate may further comprise the steps:
A) form free-pouring curtain, described curtain contain at least a can with himself or with the component of other compound reaction,
B) described curtain is contacted with a continuous matrix,
At least a component in the wherein said curtain begins reaction in the process of coating, and before coating process is finished complete reaction basically.
42., may further comprise the steps according to the described method of claim 41:
A) form free-pouring curtain, have at least in the described curtain that one deck contains first component and second component that can react to each other,
B) described curtain is contacted with a continuous matrix.
43. according to the described method of claim 41, the free-pouring curtain that it is characterized in that step a) be one compound, the free-pouring curtain of multilayer.
44. according to the described method of claim 42, it is characterized in that first component that can react to each other in the step a) and the reaction type of second component are selected from: the anionic-cationic reciprocation, radical reaction, step-reaction polymerization, addition reaction, ultraviolet induction curing reaction, electron beam-induced curing reaction, acid-base reaction, flocculation or coagulation reaction and combination thereof.
45. according to the described method of claim 42, it is characterized in that between first component in the step a) and second component be reflected in the free-pouring curtain and/or when it is applied to matrix and/or when its generation during with heating, irradiation and/or oxygen initiation.
46., it is characterized in that comprising the top layer that guarantees printing quality in the free-pouring curtain in the step a) according to the described method of claim 41.
47., it is characterized in that having at least in the multilayer curtain in the step a) the dry-coated amount of one deck to be less than 30g/m according to the described method of claim 43
2
48., it is characterized in that having at least in the multilayer curtain in the step a) the dry-coated amount of one deck to be less than 20g/m according to the described method of claim 43
2
49., it is characterized in that having at least in the multilayer curtain in the step a) the dry-coated amount of one deck to be less than 10g/m according to the described method of claim 43
2
50., it is characterized in that the dry-coated amount of the multilayer curtain in the step a) is less than 60g/m according to the described method of claim 43
2
51., it is characterized in that the multilayer curtain in the step a) contains 3 layers at least according to the described method of claim 43.
52., it is characterized in that the multilayer curtain in the step a) contains 4 layers at least according to the described method of claim 43.
53., it is characterized in that the multilayer curtain in the step a) contains 5 layers at least according to the described method of claim 43.
54., it is characterized in that the multilayer curtain in the step a) contains 6 layers at least according to the described method of claim 43.
55., it is characterized in that comprising in the multilayer curtain in the step a) one deck at least that contains at least a pigment according to the described method of claim 43.
56., it is characterized in that described pigment is selected from: clay, kaolin, talcum, calcined clay according to the described method of claim 55, calcium carbonate, titanium dioxide, satin white, synthetic polymer pigment, zinc oxide, barium sulfate, gypsum, silica, aluminium hydroxide, mica and diatomite.
57., it is characterized in that having at least one deck to contain adhesive in the free-pouring curtain of multilayer in the step a) according to the described method of claim 43.
58. according to the described method of claim 57, it is characterized in that described adhesive is selected from: styrene-butadiene latex, cinnamic acrylic ester latex, cinnamic acrylic ester-acrylonitrile latex, styrene-butadiene-acrylic ester-acrylonitrile latex, styrene-butadiene-acrylonitrile latex, styrene-maleic anhydride latex, cinnamic acrylic ester-maleic anhydride latex, polysaccharide, protein, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, cellulose derivative and their mixture.
59., it is characterized in that having at least one deck to contain at least a Optical Bleaching Agent in the free-pouring curtain of multilayer in the step a) according to the described method of claim 43.
60., it is characterized in that having at least one deck to contain at least a surfactant in the free-pouring curtain of multilayer in the step a) according to the described method of claim 43.
61., it is characterized in that having the solid matter content of one deck at least in the free-pouring curtain of multilayer in the step a) is 40wt% at least according to the described method of claim 43.
62., it is characterized in that having the solid matter content of one deck at least in the free-pouring curtain of multilayer in the step a) is 50wt% at least according to the described method of claim 43.
63., it is characterized in that having the solid matter content of one deck at least in the free-pouring curtain of multilayer in the step a) is 65wt% at least according to the described method of claim 43.
64., it is characterized in that the solid matter content in the free-pouring curtain of multilayer in the step a) is 10wt% at least according to the described method of last claim 43.
65., it is characterized in that the solid matter content in the free-pouring curtain of multilayer in the step a) is 40wt% at least according to the described method of last claim 43.
66., it is characterized in that the solid matter content in the free-pouring curtain of multilayer in the step a) is 45wt% at least according to the described method of last claim 43.
67., it is characterized in that matrix continuous in the step b) is basic paper or cardboard according to the described method of claim 41.
68., it is characterized in that the neither also not pre-press polish of pre-coating of matrix continuous in the step b) according to the described method of claim 41.
69. according to the described method of claim 41, the speed that it is characterized in that matrix continuous in the step b) is 300m/min at least.
70. according to the described method of claim 41, the speed that it is characterized in that matrix continuous in the step b) is 400m/min at least.
71. according to the described method of claim 41, the speed that it is characterized in that matrix continuous in the step b) is 500m/min at least.
72. according to the described method of claim 41, the grammes per square metre that it is characterized in that matrix continuous in the step b) from 20 to 400g/m
2
73. coating substrate that makes by the described method of claim 41.
74., it is characterized in that described coating substrate is coated paper or cardboard according to the described coating substrate of claim 41.
75. method according to claim 1, wherein said curtain forms with slit die.
76. method according to claim 1, wherein said curtain forms with sliding mould.
77. method according to claim 1 has at least one deck to contain poly(ethylene oxide) in the wherein said curtain.
78. method according to claim 1 contains poly(ethylene oxide) in the boundary layer that the matrix with applied of wherein said curtain contacts.
79. according to the described method of claim 41, wherein said curtain forms with slit die.
80. according to the described method of claim 41, wherein said curtain forms with sliding mould.
81., have at least one deck to contain poly(ethylene oxide) in the wherein said curtain according to the described method of claim 41.
82., contain poly(ethylene oxide) in the boundary layer that the matrix with applied of wherein said curtain contacts according to the described method of claim 41.
83. any described method according among the claim 1-3 is characterized in that first component in the step a) is a starch, second component is a dialdehyde.
84. according to any described method among the claim 1-3, it is characterized in that first component in the step a) is the epoxy-functional polymer, second component is an amino hardener component.
85. any described method according among the claim 1-3 is characterized in that first component in the step a) is a polyol, second component is a polyisocyanate.
86. according to any described method among the claim 1-3, it is characterized in that first component in the step a) is amino estersil, second component is the glycidol silicon ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2002/033113 WO2004035930A1 (en) | 2002-10-15 | 2002-10-15 | A method of producing a coated substrate |
| WOPCT/US02/33113 | 2002-10-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1504610A CN1504610A (en) | 2004-06-16 |
| CN100400748C true CN100400748C (en) | 2008-07-09 |
Family
ID=32041257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200310115663XA Expired - Fee Related CN100400748C (en) | 2002-10-15 | 2003-10-15 | Method for producing coating groundmass |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1411168B1 (en) |
| JP (1) | JP4943627B2 (en) |
| CN (1) | CN100400748C (en) |
| AU (1) | AU2002337877A1 (en) |
| BR (1) | BR0305488B1 (en) |
| CA (1) | CA2444936C (en) |
| WO (1) | WO2004035930A1 (en) |
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| 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 |
| FI121242B (en) * | 2004-02-25 | 2010-08-31 | Metso Paper Inc | Method and Arrangement for Coating a Paper / Cardboard Web with a Curtain Coating Machine |
| DE102004045172A1 (en) * | 2004-09-17 | 2006-03-23 | Basf Ag | Process for the preparation of single or multiple coated substrates with a coating composition comprising a binder before adhesion |
| DE102004045171A1 (en) * | 2004-09-17 | 2006-03-23 | Basf Ag | Process for the preparation of mono- and / or multicoated substrates |
| JP2006299430A (en) * | 2005-04-15 | 2006-11-02 | Voith Paper Patent Gmbh | Method for producing coated paper |
| FI121148B (en) * | 2006-09-29 | 2010-07-30 | Metso Paper Inc | Method of coating fiber web with a curtain coating device |
| DE102007030102B4 (en) * | 2007-06-28 | 2019-10-31 | Schoeller Technocell Gmbh & Co. Kg | prepreg |
| JP2009041131A (en) * | 2007-08-08 | 2009-02-26 | Oji Paper Co Ltd | Method for producing coated white paperboard and coated white paperboard |
| CN101713911B (en) * | 2008-10-06 | 2013-08-28 | 大日本印刷株式会社 | Method of producing multilayer coating film |
| FR2943075B1 (en) * | 2009-03-11 | 2013-10-11 | Arjowiggins | METHOD FOR MANUFACTURING A DECORATIVE PAPER SHEET |
| FI123465B (en) * | 2009-05-11 | 2013-05-31 | Kemira Oyj | Use of a composition for improving ink jet printing properties |
| JP5544809B2 (en) * | 2009-09-29 | 2014-07-09 | 大日本印刷株式会社 | Method for producing multilayer coating film, multilayer laminate and method for forming film between multilayer coating films |
| JP2011251523A (en) * | 2010-05-07 | 2011-12-15 | Dainippon Printing Co Ltd | Laminate and method for manufacturing laminate |
| JP5870545B2 (en) * | 2011-08-23 | 2016-03-01 | 大日本印刷株式会社 | Manufacturing method of laminate |
| JP2013049022A (en) * | 2011-08-31 | 2013-03-14 | Dainippon Printing Co Ltd | Laminate manufacturing method |
| JP2013204157A (en) * | 2012-03-27 | 2013-10-07 | Nippon Paper Industries Co Ltd | Coated white paperboard and method for producing the same |
| CN102966000B (en) * | 2012-11-23 | 2015-10-14 | 常德市武陵金德镭射科技有限公司 | Cigarette lining paper barrier coating and production method thereof |
| JP6736247B2 (en) * | 2013-03-28 | 2020-08-05 | 日本製紙株式会社 | Coated white paperboard and manufacturing method thereof |
| CN104389238A (en) * | 2014-10-09 | 2015-03-04 | 金东纸业（江苏）股份有限公司 | Papermaking method and sized paper and coated paper obtained by papermaking method |
| CN107059487A (en) * | 2017-03-22 | 2017-08-18 | 山东东宇鸿翔装饰材料有限公司 | The preparation method of 30 grams of facing papers |
| CN107597522B (en) * | 2017-09-28 | 2020-12-08 | 嘉兴泰尔顺纺织股份有限公司 | Flame-retardant waterproof coating process |
| CN109957075A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of wallpaper carboxylic styrene butadiene latex and its preparation method and application |
| CN108589401A (en) * | 2018-04-08 | 2018-09-28 | 温州创佳影像材料有限公司 | A kind of waterproof fluorescence Alhue paper and its production technology |
| US11549216B2 (en) | 2020-11-11 | 2023-01-10 | Sappi North America, Inc. | Oil/grease resistant paper products |
| CN114367415A (en) * | 2022-01-18 | 2022-04-19 | 江阴市乐事康工业设计有限公司 | Multi-coating-head interval coating process and equipment for lithium battery pole piece |
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- 2003-10-15 BR BRPI0305488-8A patent/BR0305488B1/en not_active IP Right Cessation
- 2003-10-15 EP EP03023328.2A patent/EP1411168B1/en not_active Expired - Lifetime
- 2003-10-15 CA CA2444936A patent/CA2444936C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2444936A1 (en) | 2004-04-15 |
| JP2004154773A (en) | 2004-06-03 |
| CN1504610A (en) | 2004-06-16 |
| BR0305488A (en) | 2004-06-15 |
| BR0305488B1 (en) | 2012-12-11 |
| CA2444936C (en) | 2012-07-10 |
| WO2004035930A1 (en) | 2004-04-29 |
| AU2002337877A1 (en) | 2004-05-04 |
| EP1411168B1 (en) | 2016-04-06 |
| EP1411168A1 (en) | 2004-04-21 |
| JP4943627B2 (en) | 2012-05-30 |
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