CN103080419A - Moisture-resistant corrugated cardboard - Google Patents
Moisture-resistant corrugated cardboard Download PDFInfo
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- CN103080419A CN103080419A CN2011800409855A CN201180040985A CN103080419A CN 103080419 A CN103080419 A CN 103080419A CN 2011800409855 A CN2011800409855 A CN 2011800409855A CN 201180040985 A CN201180040985 A CN 201180040985A CN 103080419 A CN103080419 A CN 103080419A
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- China
- Prior art keywords
- paper
- layer
- corrugated
- polymer
- corrugated board
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F—MECHANICAL WORKING OR DEFORMATION OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F1/00—Mechanical deformation without removing material, e.g. in combination with laminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F—MECHANICAL WORKING OR DEFORMATION OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F1/00—Mechanical deformation without removing material, e.g. in combination with laminating
- B31F1/20—Corrugating; Corrugating combined with laminating to other layers
- B31F1/24—Making webs in which the channel of each corrugation is transverse to the web feed
- B31F1/26—Making webs in which the channel of each corrugation is transverse to the web feed by interengaging toothed cylinders cylinder constructions
- B31F1/28—Making webs in which the channel of each corrugation is transverse to the web feed by interengaging toothed cylinders cylinder constructions combined with uniting the corrugated webs to flat webs ; Making double-faced corrugated cardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F—MECHANICAL WORKING OR DEFORMATION OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31F1/00—Mechanical deformation without removing material, e.g. in combination with laminating
- B31F1/20—Corrugating; Corrugating combined with laminating to other layers
- B31F1/24—Making webs in which the channel of each corrugation is transverse to the web feed
- B31F1/26—Making webs in which the channel of each corrugation is transverse to the web feed by interengaging toothed cylinders cylinder constructions
- B31F1/28—Making webs in which the channel of each corrugation is transverse to the web feed by interengaging toothed cylinders cylinder constructions combined with uniting the corrugated webs to flat webs ; Making double-faced corrugated cardboard
- B31F1/2804—Methods
- B31F1/2809—Methods characterised by the chemical composition of the glue
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/28—Polyesters
-
- 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
- D21H19/72—Coated paper characterised by the paper substrate
- D21H19/74—Coated paper characterised by the paper substrate the substrate having an uneven surface, e.g. crêped or corrugated paper
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/32—Multi-ply with materials applied between the sheets
- D21H27/34—Continuous materials, e.g. filaments, sheets, nets
- D21H27/36—Films made from synthetic macromolecular compounds
Abstract
The invention relates to a singly or multiply corrugated board glued on one or both sides, wherein at least one of the top plies or corrugations is a paper film composite comprising: i) a paper material having a grammage of 30 to 600 g/m2 and ii) a biodegradable plastic coating that is 1 to 100 [mu]m thick. The invention relates in particular to singly or multiply corrugated cardboard glued on one or both sides, wherein at least one of the top plies or corrugations is a paper film composite comprising: i) a paper material having a grammage of 30 to 600 g/m2 as an outer layer, ii) a biodegradable plastic coating that is 1 to 100 [mu]m thick as an intermediate layer, and iii) a paper material having a grammage of 30 to 600 g/m2 as an inner layer. The invention further relates to a method for producing said corrugated board.
Description
The present invention relates to comprise the single or double corrugated board of one or more corrugated layers, wherein at least one sheet lining flaggy or corrugated layer are the paper film assembly that comprises following material:
I) 30-600g/m
2The paper substrate structural material of grammes per square metre (grammage),
Ii) thickness is the biodegradable polymers coating of 1-100 μ m.
More specifically, the present invention relates to comprise the single or double corrugated board of one or more corrugated layers, wherein at least one sheet lining flaggy or corrugated layer are the paper film assembly that comprises following material:
I) 30-600g/m
2The paper substrate structural material of grammes per square metre is as skin,
Ii) thickness be the biodegradable polymers coating of 1-100 μ m as the intermediate layer, and
Iii) 30-600g/m
2The paper substrate structural material of grammes per square metre is as internal layer.
The invention further relates to the method for producing this corrugated board.
Polymer-coated paper-based products has many application, more specifically is used for its ink-jet printability and can passes through the improved paper grades of polymer coating, i.e. all printing paper, natural paper, cardboard and cardboard.In all these are used, change the surface of paper substrate structural material, such as above-mentioned application as printability or barrier propterty are actual needed.The paper-based products that is coated with biodegradable polymers (blend) is known by WO2010/034712.
Yet, have many application of the surface property that wherein in fact needs paper.In corrugated board production, untreated paper surface has obvious advantage.When corrugated layer when so-called Corrugator roller (fluted row) is produced, untreated paper surface does not adhere to.On the other hand, untreated paper substrate structural material has inadequate wet strength or grease resistance for many application.Flooding subsequently or waxing of paper causes problem in the recirculation of paper substrate structural material.
Germany prospectus DOS2124092 has described the wet strength corrugated board with the corrugation that comprises paper/polyethylene/paper structure.This embodiment is disadvantageous, because paper/polyethylene assembly is for the recirculation of using conventional method remarkable (for example passing through the described method deinking of EO09174077.9) in the newsprint situation.
Therefore, the problem that the present invention proposes is to provide has the surface property that is similar to paper, but have simultaneously wet strength, grease resistance, than high moisture and the simple corrugated board of recirculation also.
This problem solves by corrugated board of the present invention.Surfaces externally and internally has untreated paper substrate structural material.Structural reinforcing is present in assembly inside and improves barrier propterty such as moisture resistance, wet strength, water resistant steam and the grease resistance of whole assembly.
Corrugated board of the present invention also has obvious advantage and can pass through the described method recirculation of EP09174077.9 aspect recirculation.Corrugated board at first adds in the moisture waste paper suspension, with it
A) slurrying in the presence of at least a hydrolase,
B) slurrying in alkaline medium, and/or
C) in deinking process, in alkaline medium, process,
And subsequently polymer film is separated with waste paper suspension.Described method preferably described embodiment only a), b) or c) in carry out.But can also carry out any required combination of at least two embodiments.Yet described embodiment is enough to realize separating fully of biodegradable polymers and paper fiber usually.
Waste paper and from paper-based products reclaimed waste paper particular importance economically in paper industry because thus resource conservation (cellulose pulp).Term " waste paper " is based on German standard specification DIN6730, therefore be defined as by produce or processing with use or not type of service treat recirculation and as paper or the cardboard of half stuff manufacturing technique to be back to.Only in Germany, in 2003, waste paper utilization rate (feed rate), namely to account for the ratio of whole domestic paper production be 65% to waste paper.Waste paper is used as less important raw material usually in paper and production.Yet waste paper can not be by the recirculation of unlimited ground.Use under the circulation at each, fiber is owing to mechanical stress shortens, and approximately 4-6 can not reshape after circulating and be page, this has adverse effect to paper strength again.The corrugated board production utilization comprises newly-and the paper of high-grade paper fiber.This is the very little reason of waste paper ratio in the corrugated board situation.We have now found that the ratio of waste paper in the corrugated board of the present invention can significantly improve, and while assembly performance such as paper strength can maintain high level.In the paper substrate assembly, the undercoating of polymer, the undercoating of polymer page is born the important feature function or rather.
For the purpose of the present invention, term " paper-based products " comprises the paper of all kinds, more specifically cardboard and cardboard.
Fibrous raw material as these paper-based products of preparation, consider to be usually used in all quality of this purpose, for example mechanical pulp, bleaching and not bleach chemical pulp, from paper substrate paper stock and the waste paper (also being coating and uncoated broken form) of all annual plants.These fibrous raw materials can be separately or with mutual any desired mixt for the production of paper pulp, paper-based products is by described pulp production.Mechanical pulp for example comprises ground wood pulp, hot method mechanical pulp (TMP), CTMP (CTMP), pressure ground wood pulp, semi-chemical pulp, high yield chemical pulp and RMP (RMP).As chemical pulp, for example consider sulfate pulp, sulfite pulp and alkaline pulp.The annual plant that is applicable to produce paper stock for example is rice, wheat, sugarcane and mestha.
Paper pulp usually be the 0.01-3 % by weight based on dried paper stock, the sizing agent (in each case solid) of preferred 0.05-1 % by weight mixes, and they depend on the degree of sizing for the treatment of that sized paper is required.The paper substrate structural material can further comprise other materials, for example starch, pigment, dyestuff, Optical Bleaching Agent, biocide, paper reinforcing agent, fixative, defoamer, retention agent and/or filter aid.
Central polymer layer can comprise any biodegradable polymers that is usually used in Paper Coating.
Biodegradable polymers is that those skilled in the art are known and especially be disclosed in Ullmann industrial chemistry encyclopaedia (Ullmann ' s Encyclopedia of Industrial Chemistry) (online version 2009), Polymers, Biodegradable, Wiley-VCH Verlag GmbH﹠amp; Co.KG, Weinheim is in 2009, the 131 pages.More specifically, term " biodegradable polymers " comprising for the purpose of the present invention: PLA (PLA), polycaprolactone (PCL), PHA (PHA), polymerized thylene carbonate Arrcostab such as poly (propylene carbonate) (PPC) or polymerized thylene carbonate ethyl ester (PEC), shitosan and glutelin, and one or more are based on the polyester of aliphatic diol and aliphatic series/aromatic dicarboxylic acid, for example polybutylene succinate (PBS), poly-butanedioic acid tetramethylene adipate (PBSA), poly-butanedioic acid decanedioic acid butanediol ester (PBSSe), poly-adipic acid-altogether-mutual-phenenyl two acid bromide two alcohol ester (PBAT), poly-decanedioic acid-altogether-mutual-phenenyl two acid bromide two alcohol ester (PBSeT), poly-butanedioic acid-altogether-mutual-phenenyl two acid bromide two alcohol ester (PBST).Also suitable is the blend of one or more described biodegradable polymers and natural polymer such as starch, glucose, oligomeric glucosene, cellulose, cellulose derivative, lignin, shitosan, glutelin, collagen, zeins and copolyesters thereof.
As biodegradable polymers, it is more specifically for being applicable to the partially aromatic polyester of central polymer layer.Partially aromatic polyester based on aliphatic diol and aliphatic series/aromatic dicarboxylic acid also refers to polyester derivatives such as polyether ester, polyesteramide or polyether ester amides.The partially aromatic polyester comprises the not linear polyester of chain extension (WO92/09654A1).By butanediol, terephthalic acid (TPA) and aliphatic C
6-C
18Aliphatic series/aromatic polyester (for example described in WO2006/097353-56) that dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, decanedioic acid and brassylic acid form especially is suitable blend pairing.The partially aromatic polyester of preferred chain extension and/or branching.The latter by document WO 96/15173-15176,21689-21692,25446,25448 or WO98/12242 known, it is clearly by with reference to incorporating this paper into.Consider similarly the mixture of different partially aromatic polyester.
The partially aromatic polyester that is specially adapted to central polymer film is by following structure:
I) be one or more dicarboxylic acid derivatives or the dicarboxylic acids of 40-70mol% based on component i-ii, it is selected from butanedioic acid, adipic acid, decanedioic acid, azelaic acid and brassylic acid,
Ii) based on component i-ii be the terephthaldehyde acid derivative of 60-30mol%,
Iii) based on component i-ii be the C of 98-102mol%
2-C
8Aklylene glycol or C
2-C
6The oxyalkylene glycol,
Iv) based on component i-iii gross weight be cahin extension agent and/or the crosslinking agent of 0.00 % by weight-2 % by weight, it is selected from two-or polyfunctional isocyanate, isocyanuric acid ester, azoles quinoline, epoxides, carboxylic acid anhydrides and/or can form at least the branching agent (brancher) of three esters and/or amido link
V) be the organic filler of 0.00 % by weight-50 % by weight based on component i-iv gross weight, it is selected from natural or plasticized starch, natural fabric, wood powder, and/or inorganic filler, it is selected from chalk, winnofil, graphite, gypsum, conductive black, iron oxide, calcium chloride, dolomite, kaolin, silica (quartz), sodium carbonate, titanium dioxide, silicate, wollastonite, mica, montmorillonite, talcum, glass fibre and mineral fibres, and
Vi) based on component i-iv gross weight be 0.00 % by weight-2 % by weight at least a stabilizing agent, nucleator, increase sliding and releasing agent, surfactant, wax, antistatic additive, antifoggant, dyestuff, pigment, UV absorbent, UV stabilizing agent or other plastic additives.
The partially aromatic polyester of above-mentioned composition can pass through the described method of EP09174077.9 and the recirculation of excellent ground, chooses wantonly and mixes with PLA.
Specially suitable is that the melt volume speed (MVR) according to EN ISO1133 (190 ° of C, 2.16kg weight) that has is 5-50cm
3/ 10min is more particularly 5-25cm
3/ 10min, more preferably 5-12cm
3The partially aromatic polyester of/10min.
In addition, be applicable to central polymer layer especially for the copolymer mixture of following composition:
(a) 5-95 % by weight, preferred 30-90 % by weight, the more preferably biodegradable aliphatic-aromatic polyesters of 40-70 % by weight, and
(b) 95-5 % by weight, preferred 70-10 % by weight, more preferably one or more polymer of 60-30 % by weight, it is selected from PLA, polycaprolactone, PHA, shitosan and glutelin and one or more polyester based on aliphatic diol and aliphatic series/aromatic dicarboxylic acid, polybutylene succinate (PBS), poly-butanedioic acid tetramethylene adipate (PBSA), poly-butanedioic acid decanedioic acid butanediol ester (PBSSe), poly terephthalic acid-altogether-tetramethylene adipate (PBTA) for example, and
(c) bulking agent of 0-2 % by weight.
(c) bulking agent of group is carboxylic acid anhydrides such as maleic anhydride, more specifically contains the epoxy radicals copolymer for styrene-based, acrylate and/or methacrylate.Contain the epoxy radicals unit and be preferably (methyl) glycidyl acrylate.The above-mentioned type contain the epoxy radicals copolymer for example by BASF Resins B.V. with
The ADR trade mark is sold.For example
ADR4368 is particularly useful as bulking agent.
Therefore, particularly preferred copolymer mixture comprises:
(a) 20-90 % by weight, preferred 30-50 % by weight, the more preferably biodegradable aliphatic-aromatic polyesters of 35-45 % by weight,
(b) 80-10 % by weight, preferred 70-50 % by weight, more preferably one or more polymer of 65-55 % by weight, it is selected from PLA and PHA, and
(c) epoxy radicals that contains of 0-2 % by weight is gathered (methyl) acrylate.
As the PLA of (b) group, the preferred PLA with following Performance Characteristics that uses:
-be 0.5-100ml/10min according to the MVR melt volume speed of EN ISO1133 under 190 ° of C and 2.16kg, preferred 5-70ml/10min, more preferably 9-50ml/10min,
-fusing point is lower than 240 ° of C,
-glass transition temperature (Tg) is higher than 55 ° of C,
-water content is lower than 1000ppm,
-residual monomer content (lactide) is lower than 0.3 % by weight, and
-molecular weight is higher than 10000 dalton.
Preferred PLA for example is
6201D, 6202D, 6251D, 3051D are more particularly 3251D (from the PLA of NatureWorks).PLA also can comprise unique component of polymer of polymeric layer.
(b) PHA of group is mainly the copolyesters of poly--4 hydroxybutyric acid ester and poly--3-hydroxybutyrate ester, above-mentioned butyric ester and 3-hydroxyl valerate or 3-hydroxycaproic ester.Poly--the 3-hydroxybutyrate ester-altogether-the 4 hydroxybutyric acid ester is especially known by Metabolix.They are with trade name
Sell.Poly--the 3-hydroxybutyrate ester-as to be total to-3-hydroxycaproic ester is by P﹠amp; G or Kaneka are known.Poly--3-hydroxybutyrate ester for example by PHB Industrial with trade name
With by Tianan with trade name
Sell.
The molecular weight M of PHA
wBe generally 100 000-1,000 000 dalton, preferred 300 000-600,000 dalton.PHA also can comprise unique component of polymer of polymer film.
Polycaprolactone for example by Daicel with trade name
Sell.It can be used for polymeric layer with blend polymer separately or preferably.Polycaprolactone can be used as components b) use or comprise unique component of polymer of polymeric layer.
The polymerized thylene carbonate Arrcostab is interpreted as more specifically referring to polymerized thylene carbonate ethyl ester and poly (propylene carbonate).The polymerized thylene carbonate ethyl ester is the polymer that is formed by ethylene oxide and carbon dioxide.Poly (propylene carbonate) is the polymer that is formed by propylene oxide and carbon dioxide.Poly (propylene carbonate) is particularly preferred and can be used for polymeric layer separately or with other biodegradable polymers combinations.
Should understand that other biodegradable polymers also can be used for polymeric layer Zhong – individually or with other mixed with polymers ground.Find that thus advantageously these polymer also have high fluidity.
For example, find that the melt volume speed (MVR) according to EN ISO1133 (190 ° of C, 2.16kg weight) that has is 5-70cm
3/ 10min, more preferably 9-50cm
3/ 10min, even 5-25cm more preferably
3The PLA of/10min is blend pairing favourable in such blend polymer.The blend of flowable polyester and above-mentioned mobile blend polymer also is applicable to Paper Coating.
As described, biodegradable aliphatic-aromatic polyesters and blend polymer are known by WO2010034712.Not only for the composition of these polyester but also for its preparation method, the document and the list of references of wherein quoting are incorporated this paper into by reference clearly at this.
For the purpose of the present invention, when the DIN EN13432 biodegradation intensity percentage that has when any one material or composition of matter equals at least 90%, should think that this material or composition of matter satisfy " biodegradable " feature.
The general action of biodegradability is that polymer and blend polymer (hereinafter also referred to as polymer (blend)) decompose within the suitable and verifiable time interval.Degraded can enzymatic hydrolysis, mode of oxidizing and/or undertaken and can carry out mainly due to microorganism such as bacterium, yeast, fungi and Algal Effects by electromagnetic radiation such as UV radiation effects.Biodegradability can for example mix with compost and store certain hour by polymer (blend) and quantizes.According to DIN EN13432, for example, do not contain CO
2Air during compost, flow through the compost of maturation and treated compost through the temperature program(me) of circumscribed.Here, biodegradability is by the clean CO of sample release
2(the deduction sample not in the presence of the CO that discharges of compost
2Afterwards) with the releasable maximum CO of sample
2The ratio of amount (being calculated by the sample carbon content) defines with biodegradation intensity percentage.After several days compost only, biodegradable polymers (blend) demonstrates obvious degraded signal, for example conk, cracking and perforate usually.
The additive method of measuring biodegradability for example is described among ASTM D5338 and the ASTM D6400-4.
Corrugated board comprises one or two sheet lining flaggy, corrugated layer and next or a plurality of intermediate layers in multi-wall corrugated board kind situation.Depend on sheet lining flaggy/intermediate layer and the corrugated layer quantity of existence, single face corrugated board comprises one deck corrugated paper that adheres to paper or cardboard.Single corrugation double-face corrugated board comprises one deck corrugated paper that adheres between two-layer paper and the cardboard.The corrugated board of two corrugations comprises by paper or cardboard layer and adheres to each other and its free outer surface adheres to the two-layer corrugated paper of paper or cardboard layer equally separately.Corrugated board with more corrugations has similar structures.Intensity/resistance is subdivided into various and can comments in DIN55468.
Sea-freight especially utilizes the corrugated board that comprises wet strength adhesive and wet strength paper.The wet strength paper be wax or flood and/or mix with sizing agent or wet-strength resins with body.The paper of giving thus wet strength can not be recycled.Wax or correspondingly sizing agent obstruction recirculation.The sulfate pulp cardboard that is used for sheet lining flaggy and intermediate layer especially has low recirculation content.On the other hand, especially use high-and the paper fibre of new grade for production sulfate pulp cardboard, and can to reclaim these paper fibres be very significant economically.
Corrugated board of the present invention preferably includes as corrugated layer and intermediate layer or as the sulfate pulp cardboard of sheet lining flaggy, it has following structure: the polymeric layer of the polymeric layer of paper substrate structural material/comprise biodegradable polymers or preferred paper substrate structural material/comprise biodegradable polymers/paper substrate structural material.
Used sulfate pulp cardboard is preferably by following structure:
I) 30-600g/m
2, preferred 40-400, more preferably 50-150g/m
2The paper substrate structural material of grammes per square metre,
Ii) thickness is 1-100 μ m, preferred 5-80 μ m, more preferably the biodegradable polymers coating of 10-60 μ m.
The sulfate pulp cardboard that particularly preferably has following structure:
I) 30-600g/m
2, preferred 40-400, more preferably 50-150g/m
2The paper substrate structural material of grammes per square metre is as skin,
Ii) thickness is 1-100 μ m, preferred 5-80 μ m, and more preferably the biodegradable polymers coating of 10-60 μ m is as the intermediate layer, and
Iii) 30-600g/m
2, preferred 40-400, more preferably 50-150g/m
2The paper substrate structural material of grammes per square metre is as internal layer.
Two-layer or more multi-layered paper assembly (sulfate pulp cardboard) preferably uses lamination and extrusion process production.Thus should be clearly with reference to WO2010/034712 and the technique wherein described, comprise co-extrusion pressure technique.
Can be additionally with polymer or blend extruding film forming.Here, consider that tubular film extruding and chill roll pressing method are used for film production.
In the situation that thin layer, also consider to apply hot melt, the special circumstances of using as extrusion coated or dispersion.This technique is described in Ullmann, among the TSE Troller Coating.Hot melt is pumped in the mould from the raw material storage container that is preheated to about 150-200 ° of C, carries out surface applied by described mould.In the situation that winding-slit die (wind-slot die), paper web at full speed speed directly moves through die lip (die lip).Slit, the uniformity of leading paper, web speed and melt material flow determine the quality of polymeric layer.The smoothness that depends on base material, 1-5g/m
2Coating is common.Can use thus very thin extrusion coating.
Dispersion coating need not any heating before using.Application technique is similar to the application technique of the hot melt in the flat paint situation.Web speed is up to up to 3000m/min.This means that dispersion coating can also be online on paper machine.
For example also can use the solution of polymer in alcohol to carry out with polymer such as poly (propylene carbonate) coating.
Paper substrate in every layer (corrugated layer or superficial layer) and the individual layer of polymeric layer and multilayer assembly be can and significantly so that the swelling of cardboard layer minimizes.
The thickness of polymeric layer is not subjected to any specific limited in the corrugation paper web.Polymeric layer quantitatively for example be 1-100g/m
2
The paper substrate of corrugation paper web can utilize various materials, but for example paper stock or the ream wrappers of white or brown oil of vitriol salt pulpboard, half stuff, waste paper corrugating.The thickness of these paper substrates can change in wide region, for example can be up to 300g/m
2Or higher.
Paper film assembly has 31-1000g/m usually
2Gross thickness.The paper film assembly of 80-500 μ m preferably can obtain by lamination, and the paper film assembly of 50-300 μ m more preferably can obtain by extrusion coated.
Thus obtained corrugation paper web adheres to obtain the single or double corrugated board with one or two liner board paper web subsequently in a usual manner, but have two or three corrugation paper webs and one or correspondingly two the or triple wall corrugated board of two intermediate hanging face board web certainly also be fine.
The corrugated board of enhancing by polymer produced according to the invention has advantages of many conventional corrugated boards that are better than:
Corrugated board has high accumulation compressed value (stack compression value), fracture strength and the anti-intensity of exposing, and especially after being exposed to moist atmospheric conditions, is greatly improved.
Pop strength especially after being exposed to moist atmospheric conditions, is greatly improved.
Corrugated layer can be produced in two steps.In this case, but the first step comprise by extrusion coated, hot melt are used or biodegradable and recirculation use in dispersion coating polymer such coated paper web as described.
In second step, with one or more coating ply of papers in machine between 2 wide gears (fluted roller) with wave-formed mouth at about 100-200 ° of C, corrugating under the preferred 160-180 ° of C and under high speed and that they are had is typically wavy.The moulding of corrugated material and conveying are undertaken by pitch wheel in an operation.
Three layers of corrugated layer (paper/polymer/paper) can conventional equipment use as for example the described fluted roller of German prospectus DOS2124092 by pushing or the sulfate pulp cardboard of lamination and producing.Advantageously by in an operation, under corrugating on the corrugated board machine, producing the corrugated multilayer width of cloth (referring to DE2842869) by heat-sealing.
When polymeric layer was positioned at the surface, polymer can adhere to the rill tooth.In this case, polymeric layer is protected in order to avoid the direct impact of being heated prevents any adhesion by the polytetrafluorethylecoatings coatings of gear or by the attached film that can easily separate with polymeric layer.Described film for example approximately 10-50 μ m PP or HDPE work because these two kinds of polyolefinic homopolymers only very the lowland adhere to biodegradable plastics (for example PLA, PLA, PBAT, PBSeT, PBSSe, PHA, PCL, PPC).
After corrugating, the corrugation tip approximately is being coated with under 80 ° of C with hot starch solution by the applying glue unit, and corrugated surface therewith is bonded to top sheet lining flaggy subsequently.Carry out subsequently same operation for bottom sheet lining flaggy.
Can carry out other for other combinations of sheet lining flaggy and corrugated layer and adhere to operation, have the high strength cardboard of multilayer corrugated layer with production.
Replace using starch, starch and/or film-formable biodegradable dispersion such as polyester-polyurethane ester dispersion are (for example
D DS3585) mixture also can be used for adhering to.Another possibility is to use hot-melt adhesive to replace starch system.Such corrugated board is so that can improve the moisture resistance of corrugation combination.
Combination between corrugation paper web and the sheet lining flaggy also can use its skin to produce through polymer-coated corrugated layer.In this case, only the polymer surfaces of thermoinducible adhesion or welding corrugation paper web to papery or the polymer surfaces of sheet lining flaggy is possible.
Use subsequently autoamtic cutter that final cardboard paper web is cut into the size of be fit to producing, folding, die-cut and be processed into the cardboard packaging material.
Following examples are set forth the present invention and are not limited the present invention.
Embodiment 1 (two-layer corrugation)
A) produce Coated Paper:
Half batch production coating apparatus (ER-WE-PA) by main extruder A (
, 80mm Zhi Jing – 30D) and the extruder (B, C, D) of 3 60mm diameter/25D length form.With Ecoflex F BX7011 (from the approximately 2.5cm that has of BASF SE
3The poly terephthalic acid tetramethylene adipate of the MVR of/10min, all MVR values of using are hereinafter measured according to EN ISO1133 (190 ° of C, 2.16kg weight)), can under 811/min, realize the approximately throughput of 90kg/h.Main extruder (
, 80mm Zhi Jing – 30D) throughput be 190kg/h under 771/min speed.Change the throughput of extruder to realize thin layer.
Co-extrusion pressure equipment comprises the instrument for the mould co-extrusion pressure, and it allows can to regulate under the gap width 7 layers at the most of co-extrusion pressures at 1000mm Mould Breadth degree and 0.5mm.By the insert in the melt canal, can use together different layers.Described equipment configuration has the two-layer connector insert (from Cloeren, have the edge and seal) of AAABBBB form, have main extruder as extruder A and 60 extruders as extruder B.Outer A operates with 40% gross thickness, and inner layer B operates with 60% gross thickness on the cardboard.
But used paper is the corrugating paper based on 100% waste paper.
Paper with activate by flame ion unit (gas arc lamp) or corona discharge device before molten polymer contacts.
All coating are being squeezed on the cardboard under the normal contact on the chill roll of the melt temperature of 250 ° of C and 4 bar.Web speed changes between 30m/min to 200m/min.Higher speed depends on product and causes melt resonance on the semicommercial unit.
Used polyester:
Polyester 1
Polyester 2
Poly terephthalic acid decanedioic acid butanediol ester, MVR are 6.4cm
3/ 10min.
PLA
From NatureWorks's
3251D, MVR (190 ° of C, 2.16kg is according to ISO1133) is 30ml/10min.
Extrusion coated
The blend of 24% polyester 2,16% polyester 1 and 60% PLA is used for main extruder and inferior extruder A and B.Melt temperature is 258 ° of C.
Under the maximum web speed of 170m/min, obtain the average bed thickness (48% with reference to bed thickness) of 16.5 μ m.Coating only can break away from along with fibrous fracture in the cardboard matrix.The dynamic change (melt resonance) of flow instability such as throughput raising and reduction or melt web width only occurs from 240m/min.Observe low especially curving inwardly.
B) produce corrugated layer
At A) the lower paper film assembly of describing uses the intermeshing gear of two type A rills and corrugating at PTI Austria Huwell2 corrugation equipment.For corrugating, polytetrafluorethylecoatings coatings protection polymeric layer is avoided the direct effect of heat, adheres to arbitrarily gear to avoid the film assembly.Corrugating carries out under 170 ° of C.
Performance characteristic
The moisture resistance of corrugation is measured under DIN EN20187 normal atmosphere by DIN EN ISO7263 flat crush resistance (CMC).Sample has the 160x12.7mm of being of a size of, and is regulating (namely storing 48 hours under 30 ° of C and 90% relative humidity) and is not regulating lower measurement.
Table 1: flat crush resistance
| Sample | CMT(N) | Loss of strength |
| Uncoated paper is directly measured | 70.7 | ? |
| Uncoated paper is regulated | 37.7 | 47% |
| Embodiment 1, directly measures | 93.0 | ? |
| Embodiment 1, regulates | 64.0 | 32% |
The result shows in the table, even the wet strength of corrugation the first single face that is coated with biodegradable polymers is apparently higher than uncoated.In addition, starting point is obviously higher, so that obtain together obviously stronger corrugation.
Claims (7)
1. the single or double corrugated board that comprises one or more corrugated layers, wherein at least one sheet lining flaggy or corrugated layer are the paper film assembly that comprises following material:
I) 30-600g/m
2The paper substrate structural material of grammes per square metre,
Ii) thickness is the biodegradable polymers coating of 1-100 μ m.
2. the single or double corrugated board that comprises one or more corrugated layers, wherein at least one sheet lining flaggy or corrugated layer are the paper film assembly that comprises following material:
I) 30-600g/m
2The paper substrate structural material of grammes per square metre is as skin,
Ii) thickness be the biodegradable polymers coating of 1-100 μ m as the intermediate layer, and
Iii) 30-600g/m
2The paper substrate structural material of grammes per square metre is as internal layer.
3. according to claim 1 and 2 corrugated board, wherein polymer coating has one or more and is selected from following polymer: aliphatic series/aromatic polyester, aliphatic polyester, PLA, polymerized thylene carbonate Arrcostab, polycaprolactone and PHA and with the blend of natural polymer.
4. each corrugated board according to claim 1-3, wherein said layer i) and optional layer iii) comprise the waste paper of 10-100%.
5. each corrugated board according to claim 1-3, wherein said layer i) and optional layer iii) comprise 50-150g/m
2The paper of grammes per square metre.
6. the method for each paper film assembly in producing according to claim 1-5, its by by or do not come lamination preheating paper web to carry out together with polymer film by laminating adhesive.
7. the method for each paper film assembly in producing according to claim 1-5, it is undertaken by extrusion coated, wherein biodegradable polymers is used as hot melt.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10173642.9 | 2010-08-23 | ||
| EP10173642 | 2010-08-23 | ||
| PCT/EP2011/064342 WO2012025470A1 (en) | 2010-08-23 | 2011-08-22 | Moisture-resistant corrugated cardboard |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103080419A true CN103080419A (en) | 2013-05-01 |
Family
ID=44582972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800409855A Pending CN103080419A (en) | 2010-08-23 | 2011-08-22 | Moisture-resistant corrugated cardboard |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2609252A1 (en) |
| KR (1) | KR20140000212A (en) |
| CN (1) | CN103080419A (en) |
| WO (1) | WO2012025470A1 (en) |
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| CN105350382A (en) * | 2015-11-04 | 2016-02-24 | 铜陵三佳变压器有限责任公司 | High-mechanical-property insulating paper for transformers |
| CN105745378A (en) * | 2014-05-08 | 2016-07-06 | 乐金华奥斯株式会社 | Wallpaper using PLA and PHA blend resin and method for manufacturing the same |
| CN105966014A (en) * | 2016-05-03 | 2016-09-28 | 东莞市酬勤包装制品有限公司 | Fully biodegradable composite material |
| CN107208375A (en) * | 2014-09-05 | 2017-09-26 | 欧贝特信托公司 | Paper delivery medium, its manufacture method and the secure file manufactured using it |
| CN107385993A (en) * | 2017-09-05 | 2017-11-24 | 重庆泰宝纸制品有限公司 | Biodegradable coated paper and its production equipment |
| CN107574679A (en) * | 2017-08-07 | 2018-01-12 | 安徽嘉明新材料科技有限公司 | A kind of technique for producing novel environment friendly TPU tarpaulins |
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| TWI620657B (en) * | 2017-01-26 | 2018-04-11 | Chi Wah Lau | Mix hot melt adhesive and wax to seal the side cardboard |
| TWI626355B (en) * | 2015-05-13 | 2018-06-11 | 林翰謙 | A type of moisture-proof paperboard for application of food-used by using sorghum distillery residue activated carbon |
| CN108797215A (en) * | 2018-06-06 | 2018-11-13 | 青岛嘉泽包装有限公司 | A kind of processing technology of anti-tipping curl |
| WO2019047280A1 (en) * | 2017-09-05 | 2019-03-14 | 重庆泰宝纸制品有限公司 | Biodegradable coated paper and production device therefor |
| CN111877048A (en) * | 2020-08-13 | 2020-11-03 | 东莞顺裕纸业有限公司 | Flame-retardant wear-resistant corrugated paper and preparation method thereof |
| CN114075801A (en) * | 2020-08-18 | 2022-02-22 | 杭州特种纸业有限公司 | Nanometer bypass filter paper and preparation method thereof |
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| US8753481B2 (en) | 2011-06-10 | 2014-06-17 | Basf Se | Powder composition and use thereof for paper production |
| US9099286B2 (en) | 2012-12-31 | 2015-08-04 | 908 Devices Inc. | Compact mass spectrometer |
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| ITMI20131765A1 (en) * | 2013-10-23 | 2015-04-24 | Lic Packaging S P A | MULTILAYER PACKAGING SHEET IN PARTICULAR FOR FOOD PRODUCTS AND CONTAINER FOR FOOD PRODUCTS |
| WO2015108969A1 (en) | 2014-01-14 | 2015-07-23 | 908 Devices Inc. | Sample collection in compact mass spectrometry systems |
| US8921774B1 (en) | 2014-05-02 | 2014-12-30 | 908 Devices Inc. | High pressure mass spectrometry systems and methods |
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| KR102155614B1 (en) * | 2020-04-06 | 2020-09-14 | 하호 | Composition for Coating Moisture-proof or Waterproof Paper Having Excellent Strength and Paper Applied with the Same |
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- 2011-08-22 CN CN2011800409855A patent/CN103080419A/en active Pending
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| DE2842869A1 (en) * | 1978-10-02 | 1980-04-10 | Zewawell Ag & Co Kg | Corrugated cardboard laminate - composed of multi-ply plastics film core and paper outer piles, heat-bonded together |
| JP2001047532A (en) * | 1999-08-05 | 2001-02-20 | Rengo Co Ltd | Corrugated cardboard, apparatus for producing the same and food container or food packaging material made of miniaturized corrugated cardboard |
| CN1478705A (en) * | 2003-07-23 | 2004-03-03 | 北京先基合成纸业有限公司 | Colour printed composite paper board for new type packaging box and manufacturing method |
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| CN105745378A (en) * | 2014-05-08 | 2016-07-06 | 乐金华奥斯株式会社 | Wallpaper using PLA and PHA blend resin and method for manufacturing the same |
| CN107208375A (en) * | 2014-09-05 | 2017-09-26 | 欧贝特信托公司 | Paper delivery medium, its manufacture method and the secure file manufactured using it |
| TWI626355B (en) * | 2015-05-13 | 2018-06-11 | 林翰謙 | A type of moisture-proof paperboard for application of food-used by using sorghum distillery residue activated carbon |
| CN105350382A (en) * | 2015-11-04 | 2016-02-24 | 铜陵三佳变压器有限责任公司 | High-mechanical-property insulating paper for transformers |
| CN105966014A (en) * | 2016-05-03 | 2016-09-28 | 东莞市酬勤包装制品有限公司 | Fully biodegradable composite material |
| TWI620657B (en) * | 2017-01-26 | 2018-04-11 | Chi Wah Lau | Mix hot melt adhesive and wax to seal the side cardboard |
| CN107584846A (en) * | 2017-08-07 | 2018-01-16 | 安徽嘉明新材料科技有限公司 | A kind of technique of Double-face adhesive symphysis production novel environment friendly TPU tarpaulins |
| CN107574679A (en) * | 2017-08-07 | 2018-01-12 | 安徽嘉明新材料科技有限公司 | A kind of technique for producing novel environment friendly TPU tarpaulins |
| CN107385993A (en) * | 2017-09-05 | 2017-11-24 | 重庆泰宝纸制品有限公司 | Biodegradable coated paper and its production equipment |
| WO2019047280A1 (en) * | 2017-09-05 | 2019-03-14 | 重庆泰宝纸制品有限公司 | Biodegradable coated paper and production device therefor |
| CN108797215A (en) * | 2018-06-06 | 2018-11-13 | 青岛嘉泽包装有限公司 | A kind of processing technology of anti-tipping curl |
| CN111877048A (en) * | 2020-08-13 | 2020-11-03 | 东莞顺裕纸业有限公司 | Flame-retardant wear-resistant corrugated paper and preparation method thereof |
| CN114075801A (en) * | 2020-08-18 | 2022-02-22 | 杭州特种纸业有限公司 | Nanometer bypass filter paper and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140000212A (en) | 2014-01-02 |
| EP2609252A1 (en) | 2013-07-03 |
| WO2012025470A1 (en) | 2012-03-01 |
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Application publication date: 20130501 |