CN103459714A - Method for the coating of a cellulose material by using a glucan - Google Patents
Method for the coating of a cellulose material by using a glucan Download PDFInfo
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- CN103459714A CN103459714A CN201280016875XA CN201280016875A CN103459714A CN 103459714 A CN103459714 A CN 103459714A CN 201280016875X A CN201280016875X A CN 201280016875XA CN 201280016875 A CN201280016875 A CN 201280016875A CN 103459714 A CN103459714 A CN 103459714A
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- glucan
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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
- D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
-
- 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
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
-
- 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
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
Abstract
The present invention is directed to a method for coating a sheet-like cellulose containing material by applying a composition comprising at least one glucan (G), which has a beta-1,3-glycosidically linked main chain and at least one side group having a beta-1,6-glycosidic bond to the main chain, particularly Schizophyllan, and at least one solvent (S), particularly an ionic liquid, on the surface of the sheet-like material.
Description
The present invention relates to a kind of method of sheet cellulosic material as paper or COTTON FABRIC that be coated with, comprise at least one and there is β (beta)-1 by applying, the main chain that the 3-glycosidic bond connects and at least one have the β (beta)-1 that is bonded to main chain, the composition of the glucan of the side group of 6-glycosidic bond and carrying out.A kind of preferred glucan is schizophan (Schizophyllan).Described composition usually comprises at least one solvent and can be applied to the surface of cellulosic material.The invention further relates to the sheet-like fiber cellulosic material of coating.
In addition, the present invention relates to a kind ofly comprise at least one glucan, particularly schizophan, and the composition of at least one ionic liquid.
Known paper and paper products (for example cardboard) have hydrophily, in many Application Areass, are considered to shortcoming.The paper surface processes to improve hydrophobicity and the quality (for example printability, DIMENSIONAL STABILITY) of paper usually by coating or applying glue.So-called " applying glue " makes the paper surface have more hydrophobicity and prevents or postpone the water infiltration and guarantee DIMENSIONAL STABILITY.This is all important for all types of printing paper and for wrapping paper and cardboard." sizing agent " commonly used is for example rosin size, alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA).
Wherein need hydrophobic surface or the even paper on high hydrophobicity surface and the Application Areas of paper products in order to improve water and oily barrier properties and to widen thus, for ecological and economic cause, paper is existed to strong interest with bio-based coating.
In prior art usually known several dextran compounds can be used for coating and the applying glue of paper as starch.Document US7,348,065 have described a kind of coated paper that improves sliding that has, and its floating coat comprises alkene-polymers of carboxylic acid and is selected from another polymer of starch, cellulose, polyvinyl alcohol, polyacrylamide or sodium alginate.
US5,348,065 disclose a kind of method of using the catabolite treatment paper, and described catabolite is the mixture of polysaccharide derivates as the oligomer of carboxymethyl cellulose or carboxymethyl starch, wherein processes and for example can comprise dipping paper pulp or coated paper goods.
The polysaccharide be comprised of many glucose units (D-Glucose) is commonly referred to glucan.Common glucan is for example cellulose and starch.Cellulose is substantially gone up the glucose unit connected by β (beta)-Isosorbide-5-Nitrae-glycosidic bond and is formed.That starch is connected by α (alpha)-Isosorbide-5-Nitrae-glycosidic bond basically and optionally have α (alpha)-1, the glucose unit of the side chain that the 6-glycosidic bond connects forms.
There is β (beta)-1, the main chain that the 3-glycosidic bond connects and there is the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond is secreted by various fungal bacterial strains.For example, so-called " schizophan " produced by fungi schizophyllum commune (Schizophyllum commune), and described fungi is basidiomycetes, and it shows filamentous growth and especially secretes described beta-glucan products at growing period.This saccharoidal aqueous solution shows favourable biochemical characteristic (for example high viscosity, to the stability of high-rate of shear, to the stability of high temperature and high salt concentration).
Except schizophan, the organism schizophyllum commune is secreted other most of biopolymers to fluid nutrient medium, i.e. peptide hydrophobin (24kDa) and another protein (17kDa), and it also finds in fungal cell wall.
Schizophan can be described as usually to have by 3 β (beta)-1, the repetitive that the D-Glucose unit that 3-connects forms is as the polysaccharide of skeleton, one of described D-Glucose unit is by β (beta)-1, and the 6-key is connected to single D-Glucose molecule.
The structure of the repetitive of schizophan can be described by following formula:
The typical molecular weight M of schizophan
wfor approximately 510
6to approximately 2510
6g/mol.
By for example being described in EP-A271907, EP-A504673 and DE-A4012238 with the described glucan of fungi schizophyllum commune fermentation preparation.
There is β (beta)-1, the main chain that the 3-glycosidic bond connects and there is β (beta)-1, another example of the glucan of the side group of 6-glycosidic bond is so-called homopolysaccharide " Sceleroglucan ", and it is for example secreted by fungi Sclerotium rolfsii (Sclerotium rolfsii).
Many fungal bacterial strains of secreting described glucan are that those skilled in the art are known.Example comprises schizophyllum commune, Sclerotium rolfsii, pyrenomycetes (Sclerotium glucanicum), fruit living chain sclerotinia sclerotiorum (Monilinia fructigena), cold-season-type mushroom bacterium (Lentinula edodes) or Botrytis cinerea (Botrytis cinera).The fungal bacterial strain that produces glucan is further described in EP-A271907 and EP-A504673.
Schizophan usually has network structure and high molecular also thus can be for example for wherein needing high viscosity and/or increasing bonding application.Schizophan is widely studied (Fang etc., Biomacromolecules, 2005,6,3202 as viscosity modifier; Kony etc., Biophys.J., 2007,93,442).
Publication G.Martin etc., Biopolymers, 1999,49,621 have described the Fungal Protein hydrophobin and have comprised hydrophobin and the schizophyllum commune fungal culture supernatant of schizophan can form stable coatings on hydrophobicity and hydrophilic surface.
US5,215,681 have described by ultrafiltration and have wherein added polysaccharide concentrate solution prepared by the dilute polymer of surfactant.Polysaccharide for example can be Sceleroglucan or schizophan.These solution can be used as thickener, for example for hydro carbons, reclaim.
Other application comprise the stimulation of carrier and human immunity system for metal and pollutant in natural water.Schizophan is reported to and has high stability (in the aqueous solution up to 120 ℃), highly-water-soluble and poor gelling ability usually.It is nontoxic and biocompatibility is also known.In addition, schizophan has been formed fragility and weak gel by report and for the preparation of nanofibrous structures.
Purpose of the present invention is to provide a kind of new hydrophobic coated fiber cellulosic material caused the highly-filled atresia coating of water and both impermeability raisings of oil that has.This coating should be further bio-based, is preferably biodegradable.These coating cellulose-containing materials for example can be applicable in packaging material for food or as textile material.
Shockingly find can to obtain cellulosic material as the schizophan hydrophobic film on paper, particularly the film of atresia almost.Seemingly due to the network structure of schizophan, can obtain highly-filled non-porous film.
The present invention relates to a kind of method that is coated with the sheet cellulose-containing material, comprise at least one and there is β (beta)-1 by applying, the main chain that the 3-glycosidic bond connects and at least one have the β (beta)-1 that is bonded to main chain, and the composition of the glucan of the side group of 6-glycosidic bond (G) and at least one solvent (S) is to the flaky material surface and carry out.At least one glucan (G) is preferably schizophan.
The hydrophobicity of paper can be permeated and improve by block water.In addition, this Novel coating cellulosic material demonstrates the raising that stops to oil and the infiltration of other hydrophobic compounds.Find that schizophan can be used as pure bio-based coating for paper products and by the characteristic that provides hydrophobicity to improve paper products, hydrophobicity is important characteristics for paper products in many application.
The novel schizophan coating (for example schizophan film) be applied on cellulose-containing material shockingly shows the hydrophobic surface characteristic.The Novel coating method provides a kind of for example hydrophobic method of paper of raising.It can stop that water droplet infiltrates in the paper surface.The feature of new membrane also is its high stability and excellent adhesiveness.
Another advantage is that schizophan is complete bio-based polymers, and it uses renewable source and is derived from natural bioprocess technology.Therefore, Novel coating composition of the present invention can be considered to complete bio-based, 40-99% bio-based more especially, preferably 40-90% bio-based.
In order to understand the characteristic of schizophan, carried out some structural research.The interesting especially architectural feature of schizophan seemingly in water the triple helix structure and solvent as DMSO and/or NaOH (NaOH) in reversible and solvent-induced Structure Transformation between each sub-thread (random coil).
For the present invention, " being coated with (coating) " means with layer, particularly film cladding material surface.This thin layer can have for example 0.1-1, and 000 micron (μ m), preferred 0.1-500 micron, the thickness of preferred 0.5-500 micron, and can for example comprise other components as filler.The coating applied by composition also can be comprised of at least one glucan basically.
For the present invention, " glucan " is interpreted as meaning homopolysaccharide, and it only comprises (suitable words are except end group) glucose unit (D-Glucose).There is β (beta)-1, the main chain that the 3-glycosidic bond connects and there is β (beta)-1, the glucan of the side group of 6-glycosidic bond is interpreted as comprising β (beta)-1, the main chain of the glucose unit that the 3-glycosidic bond connects has with at least one the β (beta)-1 that is bonded to main chain, the side group of 6-glycosidic bond, wherein side group comprises at least one glucose unit.
Composition preferably comprises at least one and has β (beta)-1, the main chain that the 3-glycosidic bond connects has with at least one the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond (G), wherein side group is by single β-1, and the glucose unit of 6-glycosidic bond combination forms.With regard to statistics, every three unit of main chain preferably have the β-1 that is bonded to another side group, 6-glycosidic bond.Glucan used (G) more preferably has main chain, and wherein, with regard to statistics, every three unit of main chain have the β-1 that is bonded to single glucose unit, 6-glycosidic bond.The molecular weight M of the schizophan used in the present invention
wbe generally approximately 510
6to approximately 2510
6g/mol.
At least one glucan is preferably Sceleroglucan and/or schizophan, preferably schizophan.Sceleroglucan and/or schizophan, preferably schizophan is more preferably used as unique glucan component (G).
The glucan used in coating process (G) can be secreted the fungal bacterial strain preparation of glucan especially by use, described fungal bacterial strain for example is selected from schizophyllum commune, Sclerotium rolfsii, pyrenomycetes, fruit living chain sclerotinia sclerotiorum, cold-season-type mushroom bacterium and Botrytis cinerea.In addition, for example mention suitable fungal bacterial strain in EP-A271907 and EP-A504673.Glucan can be preferably by using fungal bacterial strain schizophyllum commune or Sclerotium rolfsii, more preferably schizophyllum commune and preparing.
The whole bag of tricks of such fungal bacterial strain fermentation is that those skilled in the art are known.These methods for example are described in EP-A271907, EP-A504673, DE-A4012238 and WO2003/016545, and it also mentions suitable culture medium in each case.Typically, in the first processing step, in suitable water-containing medium, cultivate fungi.In cultivating (also referred to as fermentation) process, the glucan of the above-mentioned classification of fungus secretion is to moisture zymotic fluid.Fungi for example can be cultivated in water-containing medium at the temperature of 15-40 ℃.
Especially, it is 0.1-30%w/w that glucan (G) be take based on whole compositions, preferred 0.1-10%w/w, and more preferably 0.1-5%w/w, the amount of 0.1-1%w/w is present in composition usually.
In one embodiment of the invention, composition comprises at least one solvent (S).This solvent is generally polar solvent, is preferably selected from water; Alcohol, preferably C
1-6alcohol (particular methanol, ethanol, isopropyl alcohol, butanols); Glycol (preferably butyl monoethylene glycol, butyldiglycol, butyl triethylene glycol); Ether (preferred dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl-propyl ether, ethyl propyl ether; Glycol ether); Ester (ethyl acetate, n-butyl acetate, the glycol ester based on propylene) and ionic liquid.
In preferred embodiments, solvent (S) comprises water.At least one solvent (S) is preferably water.
In preferred embodiments, the present invention relates to a kind of coating process, wherein at least one ionic liquid is as solvent (S).Ionic liquid (or mixture of two or more different ionic liquid) is preferably used as unique solvent (S).
Suitable solvent (S) also can be mixture or the combination of above-mentioned solvent.For the present invention, " solvent " can be regarded as solvent (with regard to molecular solution, colloidal solution, a differential prose style free from parallelism or gel) and/or sweller.
Preferably, it is 70-99.9%w/w that solvent (S) be take based on whole compositions, preferred 90-99.9%w/w, and the amount of 95-99.9%w/w is present in composition usually.
Composition can comprise at least one other additive (A), filler (for example calcium carbonate, powdered whiting (GCC), winnofil (PCC), potter's clay and titanium dioxide) for example, dyestuff, fluorescent whitening agent, polymer adhesive, surfactant, sizing agent is as alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), rosin.
The amount that it is 0-15%w/w that additive (A) be take based on whole compositions usually is present in composition.Additive (A) preferably with respect to glucan (G) with 0-50%w/w, preferred 0-30%w/w, more preferably the amount of 0.1-10%w/w exists.
A kind of preferred method that is coated with the sheet cellulose-containing material, by applying the composition that comprises at least one glucan (G), undertaken, wherein composition comprises following component (or being comprised of following component): 70-99.9%w/w (based on whole compositions), at least one solvent of 70-85%w/w (S) particularly, (preferred water and/or at least one ionic liquid)
0.1-30%w/w (based on whole compositions) at least one glucan (G),
(preferably schizophan and)
At least one other additive (A) of 0-15%w/w, particularly 0.1-15%w/w (based on whole compositions) optionally.
The summation of each group component of composition provided with %w/w (% by weight) is no more than 100%.
Can be used as polysaccharide as cellulosic solvent by the known various ionic liquids of prior art.Therefore, technical press, the people such as S.Zhu, Green Chem.2006, the people such as 8, the 325-327 pages and R.Swatloski, J.Am.Chem.Soc.2002,124,4974-4975 briefly described by cellulose be dissolved in ionic liquid and by add applicable precipitating agent as water, ethanol or acetone by its recuperability.As applicable ionic liquid, what mention especially is 1-butyl-3-methylimidazole
chloride (BMIMCI) and 1-allyl-3-methylimidazole
chloride (AMIMCI).In addition, use the ion liquid dissolving cellulose for example to be described in US-A2003/0157351.
WO2003/029329 has described a kind of by cellulose and molten ionic liquids are mixed and the method for dissolving cellulos in the presence of not at water or nitrogen, and described ionic liquid has small cation and halide or pseudohalide anion.WO2008/090156 relates to a kind of method of producing glucose by enzymatic hydrolysis of cellulose, and described cellulose comprises poly-atom anion ion liquid acquisition by the materials'use of lignocellulose-containing.
With regard to present patent application, ionic liquid is at the temperature below 180 ℃, to be the organic salt of liquid.Ionic liquid preferably has lower than 150 ℃, preferably lower than 100 ℃, the fusing point selected lower than 20 ℃ is more arranged.The ionic liquid even at room temperature also existed with liquid condition is such as being described in the people such as K.N.Marsh, Fluid Phase Equilibria219 (2004), and the people such as 93-98 and J.G.Huddleston, Green Chemistry2001, in 3,156-164.
Usually there are CATION and anion in ionic liquid.In ionic liquid, proton or alkyl can be transferred to anion from CATION, produce two non-charged molecules.
Therefore, can there is the balance between anion, CATION and non-charged molecule in ionic liquid used according to the invention.Ionic liquid used according to the invention has poly-atom, i.e. polyatomic anion, and it is with two or more atoms.All ionic liquids based on polyatomic anion all are applicable to method of the present invention in principle.Suitable ionic liquid for example is described in WO2008/090156.
Preferred ionic liquid is
A) salt of general formula (I):
[A]
n +[Y]
n- (I)，
Wherein n is 1,2,3 or 4, [A]+and be quaternary ammonium cation, oxygen
cATION, sulfonium cation or
cATION, and [Y]
n-it is the mixture of polyatomic monovalence, divalence, trivalent or quadrivalent anion or these anion;
B) salt-mixture of general formula (II):
[A
1]
+[A
2]
+[Y]
n-(II.a), n=2 wherein,
[A
1]
+[A
2]
+[A
3]
+[Y]
n-(II.b), n=3 wherein,
[A
1]
+[A
2]
+[A
3]
+[A
4]
+[Y]
n-(II.c), n=4 wherein,
[A wherein
1]
+, [A
2]
+, [A
3]
+[A
4]
+independently selected to [A]
+mentioned group, and [Y]
n-as above-mentioned a) middle, defined;
C) salt-mixture of general formula (III):
[A
1]
+[A
2]
+[A
3]
+[M
1]
+[Y]
n-(III.a), n=4 wherein,
[A
1]
+[A
2]
+[M
1]
+[M
2]
+[Y]
n-(III.b), n=4 wherein,
[A
1]
+[M
1]
+[M
2]
+[M
3]
+[Y]
n-(III.c), n=4 wherein,
[A
1]
+[A
2]
+[M
1]
+[Y]
n-(III.d), n=3 wherein,
[A
1]
+[M
1]
+[M
2]
+[Y]
n-(III.e), n=3 wherein,
[A
1]
+[M
1]
+[Y]
n-(III.f), n=2 wherein,
[A
1]
+[A
2]
+[M
4]
2+[Y]
n-(III.g), n=4 wherein,
[A
1]
+[M
1]
+[M
4]
2+[Y]
n-(III.h), n=4 wherein,
[A
1]
+[M
5]
3+[Y]
n-(III.i), n=4 wherein,
[A
1]
+[M
4]
2+[Y]
n-(III.j), n=3 wherein,
[A wherein
1]
+, [A
2]
+[A
3]
+independently selected to [A]
+mentioned group, [Y]
n-as above-mentioned a) middle, defined, and [M
1]
+, [M
2]
+[M
3]
+the monovalence metal cation, [M
4]
2+divalent metal, [M
5]
3+it is trivalent metal cation.
Metal cation [M in formula (III.a) to (III.j)
1]
+, [M
2]
+, [M
3]
+, [M
4]
2+[M
5]
3+the metal cation of the 1st, 2,6,7,8,9,10,11,12,13 in the periodic table of elements and 14 families normally.Suitable metal cation is Li for example
+, Na
+, K
+, Cs
+, Ag
+, Mg
2+, Ca
2+, Ba
2+, Cr
3+, Fe
2+, Fe
3+, Co
2+, Ni
2+, Cu
2+, Zn
2+and Al
3+.
The salt that preferably salt, particularly A of A group and B group are organized.
According to formula (I), (II) and appropriate ions liquid (III), be described in WO2008/090156.Be applicable to forming the CATION [A] of ionic liquid
+compound be described in DE-A10202838.These compounds preferably comprise at least one hetero atom, 1-10 hetero atom for example, and hetero atom is preferably selected from nitrogen, oxygen, p and s atom.Additionally at least one is different from other heteroatomic compounds of nitrogen preferably to comprise at least one nitrogen-atoms and suitable words.Preferably comprise at least one nitrogen-atoms, particularly preferably 1-10 nitrogen-atoms, a particularly 1-5 nitrogen-atoms, very particularly preferably 1-3 carbon atom, the especially compound of 1 or 2 nitrogen-atoms.The nitrogen compound of back can comprise other hetero atoms as oxygen, sulphur or phosphorus atoms.
Nitrogen-atoms is the suitable carrier of positive charge in the CATION of for example ionic liquid.If nitrogen-atoms is the carrier of positive charge in the CATION of ionic liquid, at first CATION can produce by quaternized nitrogen-atoms, for example ionic liquid synthetic in amine or azepine ring nitrogen.Quaternized by the protonated realization of nitrogen-atoms.Depend on protonating agent used, obtain the salt with different anions.In the situation that in quaternized, itself can not form required anion, it can realize in another synthetic step.For example, initial by ammonium halide, halide can react with lewis acid, thereby forms composite anion by halide and lewis acid.Perhaps, available required anion replaces halide ion.This can form the metal halide precipitation, utilize ion-exchanger or replace halide ion (release hydrogen halides) with strong acid and realize by adding slaine.Suitable method for example is described in Angew.Chem.2000, and 112, the 3926-3945 pages reach in the document of wherein quoting.
Preferably comprise at least one 5-or 6-unit heterocycle, the particularly compound of 5-unit heterocycle, this heterocycle has at least one nitrogen-atoms and suitable words oxygen or sulphur atom.The compound that particularly preferably comprises at least one 5-or 6-unit heterocycle, this heterocycle has one, two or three nitrogen-atoms and sulphur or oxygen atom, very particularly preferably has the compound of two nitrogen-atoms.Further preferred aromatic heterocycle.
Particularly preferred compound is that molal weight is less than 1000g/mol, very particularly preferably is less than 800g/mol, particularly is less than the compound of 500g/mol.
Preferred CATION [A]
+be selected from heterocyclic compound, for example pyridine
ion, pyridazine
ion, pyrimidine
ion, imidazoles
ion, pyrazoles
ion, imidazoline
ion, thiazole
ion, oxygen
ion, pyrrolidines
ion, imidazolidine
ion, ammonium ion, guanidine
ion, cholinium ion (cholinium ion),
ion and sulfonium cation, be described in WO2008/090156.
Useful especially imidazoles
Ion is the 1-methylimidazole
The 1-ethyl imidazol(e)
1-(1-propyl group) imidazoles
1-(1-pi-allyl) imidazoles
1-(1-butyl) imidazoles
1-(1-octyl group) imidazoles
1-(1-dodecyl) imidazoles
1-(1-myristyl) imidazoles
1-(1-cetyl) imidazoles
1,3-methylimidazole
1,3-diethyl imidazoles
The 1-ethyl-3-methylimidazole
1-(1-butyl)-3-methylimidazole
1-(1-butyl)-3-ethyl imidazol(e)
1-(1-hexyl)-3-methylimidazole
1-(1-hexyl)-3-ethyl imidazol(e)
1-(1-hexyl)-3-butyl imidazole
1-(1-octyl group)-3-methylimidazole
1-(1-octyl group)-3-ethyl imidazol(e)
1-(1-octyl group)-3-butyl imidazole
1-(1-dodecyl)-3-methylimidazole
1-(1-dodecyl)-3-ethyl imidazol(e)
1-(1-dodecyl)-3-butyl imidazole
1-(1-dodecyl)-3-octyl group imidazoles
1-(1-myristyl)-3-methylimidazole
1-(1-myristyl)-3-ethyl imidazol(e)
1-(1-myristyl)-3-butyl imidazole
1-(1-myristyl)-3-octyl group imidazoles
1-(1-cetyl)-3-methylimidazole
1-(1-cetyl)-3-ethyl imidazol(e)
1-(1-cetyl)-3-butyl imidazole
1-(1-cetyl)-3-octyl group imidazoles
1,2-methylimidazole
1,2,3-tri-methylimidazolium
1-ethyl-2, the 3-methylimidazole
1-(1-butyl)-2, the 3-methylimidazole
1-(1-hexyl)-2, the 3-methylimidazole
1-(1-octyl group)-2, the 3-methylimidazole
Isosorbide-5-Nitrae-methylimidazole
1,3,4-tri-methylimidazolium
Isosorbide-5-Nitrae-dimethyl-3-ethyl imidazol(e)
The 3-methylimidazole
The 3-ethyl imidazol(e)
3-n-pro-pyl imidazoles
3-normal-butyl imidazoles
Isosorbide-5-Nitrae-dimethyl-3-octyl group imidazoles
Isosorbide-5-Nitrae, the 5-tri-methylimidazolium
1,3,4,5-tetramethyl imidazoles
Isosorbide-5-Nitrae, 5-trimethyl-3-ethyl imidazol(e)
Isosorbide-5-Nitrae, 5-trimethyl-3-butyl imidazole
Isosorbide-5-Nitrae, 5-trimethyl-3-octyl group imidazoles
1-third-1-alkene-3-base-3-methylimidazole
With 1-third-1-alkene-3-base-3-butyl imidazole
The imidazoles be particularly useful
ion is 1,3-diethyl imidazoles
the 1-ethyl-3-methylimidazole
1-(normal-butyl)-3-methylimidazole
Preferred tertiary amine is diisopropyl ethyl amine, diethyl-tert-butylamine, diisopropyl butylamine, di-n-butyl-n-pentyl amine, N, N-di-n-butyl cyclo-hexylamine and the derivative tertiary amine by the amyl group isomers.
Particularly preferred tertiary amine be di-n-butyl-n-pentyl amine and by the amyl group isomers derivative tertiary amine.Another tertiary amine that preferably has three identical groups is triallylamine.
Can be by using C
1-18the tertiary amine example of the quaternary ammonium ion that quaternary ammonium alkylization is derivative is diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentyl amine, diethylhexyl amine, the diethyl octyl amine, diethyl-(2-ethylhexyl) amine, the diη-propyl butylamine, diη-propyl-n-pentyl amine, the diη-propyl hexyl amine, the diη-propyl octyl amine, diη-propyl-(2-ethylhexyl) amine, diisopropyl ethyl amine, diisopropyl-n-pro-pyl amine, the diisopropyl butylamine, the diisopropyl amylamine, the diisopropyl hexyl amine, the diisopropyl octyl amine, diisopropyl-(2-ethylhexyl) amine, the di-n-butyl ethylamine, di-n-butyl-n-pro-pyl amine, di-n-butyl-n-pentyl amine, the di-n-butyl hexyl amine, the di-n-butyl octyl amine, di-n-butyl-(2-ethylhexyl) amine, the N-n-butylpyrrolioine, N-sec-butyl pyrrolidines, N-tert-butyl group pyrrolidines, N-n-pentyl pyrrolidines, N, the N-dimethylcyclohexylam,ne, N, N-diethyl cyclo-hexylamine, N, N-di-n-butyl cyclo-hexylamine, N-n-pro-pyl piperidines, N-isopropyl piperidines, N-normal-butyl piperidines, N-sec-butyl piperidines, N-tert-butyl group piperidines, N-n-pentyl piperidines, N-normal-butyl morpholine, N-sec-butyl morpholine, N-tert-butyl group morpholine, N-n-pentyl morpholine, N-benzyl-N-ethylaniline, N-benzyl-N-n-pro-pyl aniline, N-benzyl-N-isopropyl aniline, N-benzyl-N-n-butyl aniline, N, N-dimethyl-para-totuidine, N, N-diethyl-para-totuidine, N, N-di-n-butyl-para-totuidine, diethyl benzyl amine, diη-propyl benzyl amine, di-n-butyl benzyl amine, diethyl phenyl amine, diη-propyl phenyl amine and di-n-butyl phenyl amine.
Particularly preferred guanidine
ion is N, N, N', N', N ", N " hexamethyl guanidine
CATION [A]
+be selected from especially the CATION of 1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene (DBN) and 1,8-diazabicyclo [5.4.0], 11-7-alkene (DBU).
In above-mentioned heterocycle CATION, imidazoles
ion, imidazoline
ion, pyridine
ion, pyrazoline
ion and pyrazoles
ion is preferred.Imidazoles particularly preferably
the CATION of ion and DBU and DBN.
About anion, can use in principle all poly-atom anion, i.e. polyatomic anion (anion with two or more atoms).
Preferred anion [Y]
n-be selected from pseudohalide and halogen contained compound, sulfate radical, inferior sulfate radical; sulfonate radical, phosphate radical, phosphonate radical; orthophosphite, the anion of hydroxycarboxylic acid, saccharic acid, asccharin root (saccharinate) (salt of benzoic sulfimide); borate, carbonate, carbonic acid ester; silicate; esters of silicon acis, imidodicarbonic diamide (carboxylmide), two (sulfonyl) imines; the sulfonyl acid imide; methide, alkanol root, fragrant and mellow; sulphur hydrogen root; poly-sulphur root, poly-sulphur hydrogen root (hydrogenpolysulfide) and mercaptan root, described in WO2008/090156.
The anion of ionic liquid [Y]
n-for example be selected from pseudohalide and the halogen contained compound of following formula: BF
4 -, PF
6 -, CF
3sO
3 -, (CF
3sO
3)
2n
-, CF
3cO
2 -, CCl
3cO
2 -, CN
-, SCN
-, OCN
-.
Preferred anion for example is selected from pseudohalide and halogen contained compound, carboxylate radical, sulfate radical, inferior sulfate radical and sulfonate radical and phosphate radical.
Preferred anion [Y]
n-formate, acetate, propionate, butyric acid root, lactate, asccharin root, carbonate, bicarbonate radical, sulfate radical, inferior sulfate radical, C
1-C
4alkyl sulfate, methanesulfonate, tosylate, trifluoroacetic acid root, C
1-C
4acidic phosphates root and bisulfate ion.Particularly preferred anion is selected from formate (HCOO
-), acetate (CH
3cOO
-), propionate (CH
3cH
2cOO
-), carbonate, bicarbonate radical, sulfate radical, inferior sulfate radical, tosylate, methanesulfonate (CH
3sO
3 -) and methoxyl group sulfonate radical (CH
3oSO
3 -).
Anion [Y]
n-most preferably be acetate (CH
3cOO
-).
The ionic liquid that is applicable to the inventive method is commercially available, for example, from the trade name of BASFAktiengesellschaft
the example that can be advantageously used in the commercial ionic liquid in the inventive method is the 1-ethyl-3-methylimidazole
mesylate (EMIM CH
3sO
3, Basionic ST35), 1-butyl-3-methylimidazole
mesylate (BMIM CH
3sO
3, BasionicST78), methylimidazole
disulfate (HMIM HSO
4, Basionic AC39), the 1-ethyl-3-methylimidazole
disulfate (EMIM HSO
4, Basionic AC25), 1-butyl-3-methylimidazole
disulfate (BMIM HSO
4, Basionic AC28), the 1-ethyl-3-methylimidazole
acetate (EMIM acetate, Basionic BC01), 1-butyl-3-methylimidazole
acetate (BMIM acetate, Basionic BC02).
1-ethyl-3-methylimidazole particularly preferably
acetate (EMIM), 1,3-diethyl imidazoles
acetate and 1-butyl-3-methylimidazole
acetate.
The present invention preferably relates to a kind of coating method of sheet cellulose-containing material as defined above, comprises the steps:
A) preparation comprises at least one glucan (G) and at least one solvent (S), the composition of preferred ion liquid;
The composition that b) will obtain in a) in step is applied on the sheet cellulose-containing material by film forming;
C) dry described film optionally.
In a preferred embodiment of the invention, will comprise at least one glucan (G) and be applied on the sheet-like fiber cellulosic material as the composition of at least one ionic liquid of solvent (S).Glucan (G) is preferably dissolved in ionic liquid.
For the present invention, term " dissolving " (" solution " or " solubilising ") is to point to liquid conversion and comprise the solution that produces the glucan material and to the conversion of different solubilising states.If the glucan material converting is the solubilising state, each polymer molecule not necessarily needs by the solvation shell, to be surrounded fully.Importantly glucan is because solubilising becomes liquid condition.Therefore, the hydrotrope on meaning of the present invention also comprises colloidal solution, a differential prose style free from parallelism, gel etc.If remain undissolved material, this success to coating process of the present invention is not critical usually.
Can use those skilled in the art in principle known method composition is applied on the sheet cellulose-containing material.Preferably use the method that is selected from dip-coating, spraying, roller coat, extruding and blade coating to apply composition.Applying composition can use at least one known applying glue or apparatus for coating to carry out as scraper-type coating machine, air knife, doctor knife coater, applying glue press, film press press, trist coater, bill blade, inversion type knife type coater and roll-type knife type coater (roller blade).
The glucan film, preferably the schizophan film can be by directly applying described composition to flaky material, for example uses one of above-mentioned coating process and obtain.
In another embodiment, at first the glucan film is used one of above-mentioned applying method and/or device to form on material for transfer, and then described film is transferred on the sheet cellulose-containing material.
Described material for transfer is preferably hydrophobicity polymeric material (for example polymer foil), for example polyethylene, polypropylene, polybutene, polysiloxanes,
with
The present invention be more particularly directed to a kind of method of above-mentioned coating sheet cellulose-containing material, wherein apply composition and undertaken by following steps to the sheet cellulose-containing material:
The composition that b1) by film forming, will comprise at least one glucan (G) and at least one solvent (S) is applied on the hydrophobicity material for transfer; Wherein material for transfer preferably comprise be selected from polyethylene, polypropylene, polybutene, polysiloxanes,
with
polymer (consisting of);
B2) optionally will be at step b1) in the film that obtains be exposed at least one solvent (S), preferred C
1-6alcohol, preferred alcohol;
B3) will be at step b2) in the film that obtains be transferred on the sheet cellulose-containing material, preferably by roll extrusion and/or extruding, undertaken.
The gained film can be exposed to at least one solvent (S) (step b2), described solvent (S) is preferably selected from water; Alcohol (preferred C
1-6alcohol, particular methanol, ethanol, isopropyl alcohol, butanols); Glycol (preferably butyl monoethylene glycol, butyldiglycol, butyl triethylene glycol); Ether (preferred dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl-propyl ether, ethyl propyl ether; Glycol ether) and the mixture of ester (ethyl acetate, n-butyl acetate, the glycol ester based on propylene) or described solvent, more preferably C
1-6alcohol, more preferably ethanol.Especially, in this step from film part or almost completely remove ionic liquid.
Film is transferred to the sheet cellulose-containing material and can preferably by the material for transfer that will have the glucan film, is placed on flaky material and carries out from material for transfer, and wherein the film side is placed and roll extrusion and/or extrded material towards cellulose-containing material.
Optionally, at step b3) remove afterwards material for transfer from film.
The glucan film also can be stable self-supported membrane.In one embodiment of the invention, at step b1) and/or step b2) in the glucan film that obtains can separate with material for transfer, preferably by peel off the glucan film from material for transfer, undertaken.The present invention relates to a kind of above-mentioned coating process, wherein film separated with material for transfer and be transferred to subsequently the sheet cellulose-containing material.Optionally, the glucan film can be with dry before or after material for transfer separates.
Thus, the present invention relates to a kind of method of producing the glucan film, comprise the following steps:
I) will comprise at least one by forming the glucan film and there is β (beta)-1, the main chain that the 3-glycosidic bond connects has with at least one the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond (G) and at least one solvent (S), preferably the composition of at least one ionic liquid is applied on the hydrophobicity material for transfer; Wherein material for transfer preferably comprise be selected from polyethylene, polypropylene, polybutene, polysiloxanes,
with
polymer (consisting of);
Ii) optionally gained glucan film is exposed to at least one solvent (S), preferably C
1-6alcohol, more preferably ethanol;
Iii) gained glucan film is separated with material for transfer, preferably undertaken by peel off the glucan film from material for transfer;
Iv) dry gained glucan film optionally.
In addition, the present invention relates to a kind of (beta)-1 that there is β of comprising, the main chain that the 3-glycosidic bond connects has the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond (G) or consisting essentially of self-supported membrane with at least one.The present invention preferably relates to a kind of self-supporting schizophan film.The present invention relates to a kind of glucan film that can obtain by the method for above-mentioned production glucan film.
Especially, the sheet cellulose-containing material is selected from paper, cardboard, drawing paper and COTTON FABRIC.The present invention preferably relates to a kind of method, wherein the sheet cellulose-containing material be selected from paper, cardboard, drawing paper and COTTON FABRIC and wherein coating to obtain film thickness be 1-1,000 μ m, preferably 10-200 μ m, the more preferably coating layer of 1-100 μ m.
For the present invention, " paper " or " paper products " means fiber, particularly machinery or the flaky material of chemically treated string, wherein paper sieves by use usually, particularly at other additives of interpolation, makes the fiber suspension fluid dewatering under as filler, dyestuff or sizing agent and forms.For the present invention, " paper " or " paper products " can be regarded as carte paper (for example printing paper), wrapping paper (for example cardboard, corrugated board), family expenses and sanitary paper and speciality paper.Paper products can be characterized by its area associated weight (site-related weight).According to DIN6730, paper has the 225g/m of being less than or equal to usually
2the area associated weight, cardboard has the 225g/m of being greater than
2the area associated weight.
The gained coating layer preferably has 1-1,000 μ m, preferably 10-200 μ m, the more preferably film thickness of 1-100 μ m.
In addition, the present invention relates to a kind of composition, it comprises:
I) at least one has β (beta)-1, the main chain that the 3-glycosidic bond connects has with at least one the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond (G), preferably schizophan and/or Sceleroglucan, most preferably schizophan;
Ii) at least one ionic liquid; With
Iii) at least one other additive (A) optionally.
Particularly preferably above about the described component of coating process (glucan (G), solvent (S), additive (A)).
Composition preferably comprises at least one and is selected from the 1-ethyl-3-methylimidazole
acetate (EMIM), 1,3-diethyl imidazoles
acetate and 1-butyl-3-methylimidazole
the liquid of acetate.
Especially, glucan (G), preferably the amount of schizophan is 0.1-30%w/w, preferably 0.1-10, more preferably 0.1-5%w/w, most preferably 0.1-3%w/w (based on whole compositions).
In addition, the present invention relates to a kind of coating sheet cellulose-containing material that comprises coating layer, it comprises at least one and has β (beta)-1, and the main chain that the 3-glycosidic bond connects has the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond with at least one.Preferably above about the described glucan of coating process (G), particularly coating layer, comprise (preferably substantially consisting of) schizophan and/or Sceleroglucan, preferably schizophan.
It is 1-1 that flaky material preferably comprises thickness, 000 micron (μ m), preferably 10-200 μ m, the more preferably coating layer of 1-100 μ m.
The invention further relates to a kind of sheet cellulose-containing material, it comprises the coating layer that can obtain by said method.
Coating sheet cellulose-containing material preferably demonstrates hydrophobic surface.For the present invention, hydrophobic surface or hydrophobic coating mean surface and demonstrate contact angle (CA) value of measuring with respect to water higher than 100 °, wherein higher than the contact angle of 100 °, stablize at least 60 seconds, and preferably at least 100 seconds, more preferably at least 180 seconds.
In addition, the present invention relates to described coating sheet cellulose-containing material as packaging material for food as all types hydrophobic surface paper and the paper products purposes as coffee cup, paper disc, sandwich paper.
In addition, (beta)-1 that the present invention relates to there is β, the main chain that the 3-glycosidic bond connects has with at least one the β (beta)-1 that is bonded to main chain, and the glucan of the side group of 6-glycosidic bond is in coating sheet cellulose-containing material, the preferably purposes in paper products.The purposes of the purposes of preferred above-mentioned glucan, particularly schizophan.
The present invention describes in more detail by following examples.
Embodiment 1: prepare schizophan:
Schizophyllum commune is for test, and as described as " Udo Rau, Biopolymers, editor A.Steinb ü chel, WILEY-VCH Publishers, 2002, the 6 volumes, 63-79 page ", prepared by schizophan in batch fermentation.Fermentation time is approximately 96 hours.By this zymotic fluid of 99.6kg (=charging), introduce in container and by pump at 7m
3under the cycle rate of/h, under 4 bar pressures, circulate 45 minutes.The analyzing container content and record 9.8 gram schizophans/liter content.
Then setting cycle rate is 5.1m
3/ h also applies the transmembrane pressure of 1.1 bar.The cross-film flow velocity is 5m/s.The inherent filtration device module penetrant out of collecting and weigh.In first 10 minutes processes of test, obtain the 0.75kg penetrant.This is equivalent to 20.4kg/h/m
2permeate flow.Transmembrane pressure is 2.9 bar.Filter operation 16 hours.
Recording beta-dextran content is the 8.97g/l glucan.Fungal Protein do not detected in purification zymotic fluid used, particularly hydrophobin.
Embodiment 2: separate and the sign schizophan
By concentration be 4 and the aqueous solution obtained as embodiment 1 of 8.97g/l beta-dextran content pour in ethanol with the precipitation schizophan.
By sedimentation and filtration drying or freeze drying in vacuum drying chamber.Obtain half-dried gel-like material, by material at air drying.Depend on analytical method, to drying material or gel, carry out structural research.By freezing-SEM (scanning electronic microscope) and freezing-TEM (transmission electron microscope) with gel in ethanol and by IR (infrared spectrum) and CP-MAS NMR (cross polarization magic-angle-spinning nuclear magnetic resonance wave spectrum) with the dried forms analysis of material.
As described in Example 3 paper and coating with film by using not xerogel shape material (gel) to prepare.The paper and coating as described in Example 4 that uses ionic liquid with film by use not xerogel shape material (gel) and on air half dry xerogel prepare.
Partial gel is dry to obtain hard solid material in vacuum drying chamber.When water is removed fully from structure, form hydrogen bond and form more macrostructure body between each polymer chain, be i.e. aggregation.Find that gel-like material demonstrates the dissolubility better than absolutely dry material.The water that gel contains significant quantity, this makes operation more feasible, and this material can be used in paper and coating research thus.
The result of structural research is summarized as follows: by drying the solid-state CP-MAS NMR of stores record.Find that the schizophan structure has rigidity, forms also visible triple helices structure in XRD (powder x-ray diffraction).This triple helices is almost ideal rigidity seemingly, up to 510
5the molecular weight of g/mol.
Find out this height rule structure and the crystallization accumulation of drying material in CP-MAS NMR (cross polarization evil spirit angle rotation NMR) wave spectrum.The molecule of other secretions that exist further symbolize some impurity and schizophan in CP-MAS NMR wave spectrum in (for example, for example, by mycetogenetic protein (hydrophobin)).
For the possible network structure that makes schizophan, specialize, in ethanol, gel is taken freezing-TEM and freezing-SEM image.Sample demonstrates netted loose structure and array long fiber in addition.As if fibre length is extraordinary in the hundreds of micron, has narrow diameter and high aspect ratio.Embodiment 3: the schizophan coating of paper
By use, be
the layer or
to prepare as described in Example 2 by the polymer film of paper (hydrophobicity material for transfer) is applied on printing paper commonly used and uncoated body paper containing the schizophan gel.
Following different paper is coated with for schizophan as base paper (basis paper):
Base paper I: body paper (uncoated paper that comprises birch pulp/pine slurry 70:30)
Base paper II: standard printing paper (coated paper, Future multitech)
The schizophan gel is squeezed in to paper and film
or
between and make its drying.After drying, remove
or
film.
Obtain the glossy film of schizophan on the paper surface.In order to study the hydrophobicity of these films, measure contact angle (CA) and the time m-dependence CA, with table 1 and Fig. 1, conclude as described in Example 5.
In addition, by SEM scanning electron microscope analysis gained desciccator diaphragm, as described in Example 6, wherein measure the film Shape and thickness.
Embodiment 4: the schizophan coating of paper, use the composition that comprises schizophan and ionic liquid
Penetrant (8.97g/l glucan) the dilute with water 1:1 that 1L is mixed according to the glucan of embodiment 1 also pours in 2L ethanol.Filter and suppress precipitation.The schizophan that 8.24g is contained to alcohol-water is dissolved in 412g ionic liquid 1-ethyl-3-methylimidazole under 85 ℃
spend the night to obtain the solution of about 2%w/w schizophan in acetate (EMIM).Correspondingly use the solution for preparing about 2%w/w schizophan at the half-dried gel schizophan material (referring to embodiment 2) of air drying.
Then use scraper that solution is applied to PE (polyethylene) plastic film.Following different scraper is for obtaining film: 150 μ m, 200 μ m, 500 μ m and 1200 μ m.
The PE film that will have a schizophan coating is put into ethanol with from film released ion liquid.Then, the film by gained containing schizophan is transferred on printing paper, wherein the PE-plastic film is placed to the base paper (base paper I and II) that has the glucan film on the paper side and above and by extruding the glucan film is transferred on paper.Remove the PE-film.The glucan film shifted is at room temperature dry.Gained demonstrates the approximately thickness of 4 μ m containing the film S1 of schizophan, by determination of electron microscopy, as described in Example 6.
Following different paper is coated with for schizophan as base paper:
Base paper I: body paper (uncoated paper that comprises birch pulp/pine slurry 70:30)
Base paper II: standard printing paper (coated paper, Future multitech)
The the second film S2 containing schizophan obtained as mentioned above is placed on the first desciccator diaphragm.Gained schizophan film S2 demonstrates the approximately thickness of 8 μ m.In addition, prepared by with 200 μ m scrapers, applying 3 gained monofilms altogether by the coated paper sample.This gained schizophan film S3 demonstrates the approximately thickness of 12 μ m.
The film (S3) containing schizophan that the thickness obtained by scraper 200 μ m/20cm is 12 μ m is for oily penetration testing, as described in Example 7.
In addition, contact angle (CA) measurement result that the schizophan coating that the thickness that measurement obtains by scraper 200 μ m/20cm as mentioned above as described in Example 5 is 4 μ m (S1) and 12 μ m (S3) obtains, and be summarized in table 1 and Fig. 1.
Embodiment 5: contact angle (CA) is measured
As the hydrophobic stability of schizophan film on the base paper of preparation as described in embodiment 3 and 4 by the time m-dependence CA measure.Placing 3 drips respectively and paper surface, film Surface Contact.Measured contact angle every 1 second, measure 120 seconds.Measurement is carried out 3 times.Be summarized in 0 second, 10 seconds, 60 seconds and 100 seconds contact angle results afterwards in table 1.Fig. 1 demonstrates time dependence contact angle (CA).
In addition, measure the time dependence contact angle of following base paper used:
I) base paper I: body paper (uncoated paper that comprises birch pulp/pine slurry 70:30)
Ii) base paper II: standard printing paper (coated paper, Future multitech)
The front and back of testing standard printing paper (base paper II).
The contact angle of further finding the schizophan coating is almost both identical with base paper I used and II.
Table 1: time dependence contact angle
In the situation that not mentioned contact angle, water droplet absorbs fully from surface.
Result further is shown in Fig. 1.Fig. 1 illustrates base paper and schizophan coated paper by using the time dependence contact angle (CA) of water droplet.
Fig. 1 explanation:
The x-axle: time t, show with stopwatch
Y-axle: with respect to the contact angle CA of water, mean with ° (degree)
Hollow square (): sample 5
Black triangle (▲): sample 6
Solid diamond (◆): sample 2
Closed square (■): sample 3
Open diamonds (◇): sample 4
Cross (x): sample 1
Usually be considered to hydrophobic with respect to the CA value of water gaging higher than the material of 100 °.Demonstrate untreated cellulose surface (paper) and absorb very fast water, as seen in Figure 1.Curve with cross (x) means the contact angle (CA) of uncoated body paper (base paper I).Curve with solid diamond (◆) and closed square (■) demonstrates the time m-dependence contact angle (CA) of uncoated printing paper (base paper II).The initial hydrophobicity of base paper II is almost the same with the schizophan coated paper, but the hydrophobicity of untreated paper significantly descended after 20 seconds.Can find out the upper water droplet contact angle in surface descend very fast and water droplet in several seconds to maximum 100 seconds almost completely from the paper Surface absorption.
Yet the hydrophobicity of different schizophan coating surfaces (being meaned by hollow square (), black triangle (▲) and open diamonds (◇)) keeps constant at least 180 seconds.Can be found out by Fig. 1 and table 1, for the schizophan coated paper, contact angle keeps roughly the same with the reading minimum reduced along with the time.Contact angle descended general 3 ° in 60 seconds.This obviously shows the hydrophobicity of membrane.
In order to find out the impact of surface roughness and possibility orientation factor, the schizophan film on mechanical friction paper.After this is processed, then measure the CA value, obtain and roughly the same before result.These results confirm the stability of schizophan film antagonism mechanical stress and do not have the orientation of schizophan film.
Embodiment 6: characterize schizophan coating on paper
As the form of the schizophan coating that obtained according to embodiment 4 by scanning electronic microscope (SEM) research.Find out that the schizophan coating, for than smooth surface, has the film thickness of increase.In the part of thick coating, the form of this film is very smooth therein, covers the filamentary structure of uncoated paper fiber fully.Obviously find out that schizophan can form the uniform films with constant form on paper.The hydrophobicity that the form of film is very well set forth paper improves, because this film serves as, stops that water droplet infiltrates the interior obstacle of filamentary structure of paper.
From the middle cutting sample of coated paper.This test specimen is embedded in the Epofix resin.At room temperature at first cutting embeds test specimen and uses the electron microscope photographic images, wherein uses scanning electronic microscope (SEM), Hitachi4700,2kV.
Embodiment 7: oily penetration testing
The paper that will have the size 10x10cm of lattice is placed on bottom.Place obstacle coated sample (for example schizophan coated paper), coating is on lattice paper.The blotting paper that final layer is size 10x10cm.
2ml oleic acid dropwise is applied on blotting paper and (for example uses pipette).During 3 ply of papers are placed on to drying box together at 60 ℃ of temperature.Counted painted number of squares on lower floor's paper after 1 hour, 2 hours and 16 hours under 60 ℃.Estimate the painted gross area.The results are shown in table 2.
Table 2: oily penetration testing
These tests show that the paper that is coated with the schizophan layer shows excellent grease resistance than untreated paper.
Claims (15)
1. a method that is coated with the sheet cellulose-containing material, comprise at least one and there is β (beta)-1 by applying, the main chain that the 3-glycosidic bond connects and at least one have the β (beta)-1 that is bonded to main chain, and the composition of the glucan of the side group of 6-glycosidic bond (G) and at least one solvent (S) is to the flaky material surface and carry out.
2. according to the process of claim 1 wherein that at least one glucan (G) is schizophan.
3. according to the method for claim 1 or 2, the composition that wherein applied comprises at least one solvent of 70-99.9%w/w (S), at least one glucan of 0.1-30%w/w (G), and at least one other additive (A) of 0-15%w/w optionally.
4. according to the method for any one in claim 1-3, wherein at least one ionic liquid is as solvent (S).
5. according to the method for any one in claim 1-4, it comprises the steps:
A) composition that preparation comprises at least one glucan (G) and at least one solvent (S);
The composition that b) will obtain in a) in step is applied on the sheet cellulose-containing material by film forming;
C) dry described film optionally.
6. according to the method for any one in claim 1-5, wherein apply composition and undertaken by following steps to the sheet cellulose-containing material:
The composition that b1) by film forming, will comprise at least one glucan (G) and at least one solvent (S) is applied on the hydrophobicity material for transfer;
B2) optionally will be at step b1) in the film that obtains be exposed at least one solvent (S);
B3) will be at step b2) in the film that obtains be transferred on the sheet cellulose-containing material.
7. according to the method for any one in claim 1-6, wherein the sheet cellulose-containing material be selected from paper, cardboard, drawing paper and COTTON FABRIC and wherein coating to obtain film thickness be 1-1, the coating layer of 000 μ m.
8. according to the method for any one in claim 1-7, wherein use the method that is selected from dip-coating, spraying, roller coat, extruding and blade coating to apply composition.
9. a composition, it comprises:
I) at least one has β (beta)-1, and the main chain that the 3-glycosidic bond connects has the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond (G) with at least one;
Ii) at least one ionic liquid; With
Iii) at least one other additive (A) optionally.
10. according to the composition of claim 9, wherein at least one ionic liquid is selected from the 1-ethyl-3-methylimidazole
acetate (EMIM), 1,3-diethyl imidazoles
acetate and 1-butyl-3-methylimidazole
acetate.
11., according to the composition of claim 9 or 10, wherein the amount of glucan (G) is 0.1-30%w/w.
12. a coating sheet cellulose-containing material that comprises coating layer, it comprises at least one and has β (beta)-1, and the main chain that the 3-glycosidic bond connects has the β (beta)-1 that is bonded to main chain, the glucan of the side group of 6-glycosidic bond with at least one.
13., according to the coating sheet cellulose-containing material of claim 12, wherein flaky material comprises the coating layer that thickness is 1-1000 μ m.
14. a coating sheet cellulose-containing material, it comprises the coating layer that can obtain by the method according to any one in claim 1-8.
15. have β (beta)-1, the main chain that the 3-glycosidic bond connects has with at least one the β (beta)-1 that is bonded to main chain, the purposes of the glucan of the side group of 6-glycosidic bond in coating sheet cellulose-containing material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11160162.1 | 2011-03-29 | ||
| EP11160162 | 2011-03-29 | ||
| PCT/EP2012/055510 WO2012130880A1 (en) | 2011-03-29 | 2012-03-28 | Method for the coating of a cellulose material by using a glucan |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103459714A true CN103459714A (en) | 2013-12-18 |
Family
ID=45929518
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280016875XA Pending CN103459714A (en) | 2011-03-29 | 2012-03-28 | Method for the coating of a cellulose material by using a glucan |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2694731A1 (en) |
| JP (1) | JP2014511946A (en) |
| CN (1) | CN103459714A (en) |
| BR (1) | BR112013023849A2 (en) |
| CA (1) | CA2829042A1 (en) |
| WO (1) | WO2012130880A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107148431A (en) * | 2014-10-31 | 2017-09-08 | 温特沙尔控股有限公司 | Method for concentrating beta glucan |
| CN112888713A (en) * | 2018-09-07 | 2021-06-01 | 国家科学研究中心 | Functionalization and enhancement of cellulosic material in dry and wet states by oxidized polysaccharides |
| US20220228321A1 (en) * | 2015-10-26 | 2022-07-21 | Nutrition & Biosciences Usa 4, Inc | Polysaccharide coatings for paper |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9162998B2 (en) | 2011-12-13 | 2015-10-20 | Basf Se | Preparation of 5-hydroxymethylfurfural (HMF) from saccharide solutions in the presence of a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short) |
| WO2014207100A1 (en) * | 2013-06-27 | 2014-12-31 | Basf Se | A process for coating paper with cellulose using a solution containing cellulose |
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- 2012-03-28 JP JP2014501592A patent/JP2014511946A/en active Pending
- 2012-03-28 CN CN201280016875XA patent/CN103459714A/en active Pending
- 2012-03-28 EP EP12712101.0A patent/EP2694731A1/en not_active Withdrawn
- 2012-03-28 WO PCT/EP2012/055510 patent/WO2012130880A1/en active Application Filing
- 2012-03-28 CA CA2829042A patent/CA2829042A1/en not_active Abandoned
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| CN112888713A (en) * | 2018-09-07 | 2021-06-01 | 国家科学研究中心 | Functionalization and enhancement of cellulosic material in dry and wet states by oxidized polysaccharides |
| CN112888713B (en) * | 2018-09-07 | 2022-10-28 | 国家科学研究中心 | Functionalization and enhancement of cellulosic material in dry and wet states by oxidized polysaccharides |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014511946A (en) | 2014-05-19 |
| EP2694731A1 (en) | 2014-02-12 |
| BR112013023849A2 (en) | 2019-09-24 |
| CA2829042A1 (en) | 2012-10-04 |
| WO2012130880A1 (en) | 2012-10-04 |
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