Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
  • D21H27/001—Release paper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
  • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F16/04—Acyclic compounds
  • C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—Saturated oxiranes
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/40—Adhesives in the form of films or foils characterised by release liners
• • 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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
• • 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
• • 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
  • D21H21/50—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 form
  • D21H21/52—Additives of definite length or shape
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2429/00—Presence of polyvinyl alcohol
  • C09J2429/005—Presence of polyvinyl alcohol in the release coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2431/00—Presence of polyvinyl acetate
  • C09J2431/005—Presence of polyvinyl acetate in the release coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2453/00—Presence of block copolymer
  • C09J2453/005—Presence of block copolymer in the release coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2471/00—Presence of polyether
  • C09J2471/005—Presence of polyether in the release coating
• • 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
  • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
• • 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
  • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • D21H19/10—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
  • D21H19/32—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 obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
• • 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
  • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
  • D21H25/08—Rearranging applied substances, e.g. metering, smoothing; Removing excess material
  • D21H25/12—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod
  • D21H25/14—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod the body being a casting drum, a heated roll or a calender

Definitions

• the present invention concerns a method and a composition according to patent Claim 1, for modification of fibrous substrate material.
• An object of the invention is to provide a novel repellent, and regulated by surface adhesion characteristics, fibrous material with a novel composition and a method, where a polymer component is spread on the surface of the fibers.
• the object of the invention is to provide cellulose based fiber material composition, which has the character described previously.
• Further particular object of the invention is to provide a material composition applicable as backing paper of labels so-called release paper, which has advantageous and regulating release characteristics, is easy and advantageous to prepare, in addition, is recyclable and can be prepared among others from recycled fibers if needed.
• fibrous materials Due to the structure of fibrous materials, they usually have tendency to absorb foreign liquid, gel-like or gluey substances, generally fluids, on their surface or inside the fiber structure for example under the influence of capillary forces. Structure of the surface is usually also irregular. Consequently, in the preparation of fiber materials, such as paper or paper board, is traditionally used surface coating methods by which the surface of the material can be modified for instance to smooth, capillary penetration can be hindered, or for example adhesion of glue substances can be regulated. As examples can be mentioned coated printing paper, where the surface of the fiber material is blocked and smoothened with latex type mixtures of polymer and filler and typically with 1-5 ⁇ m layer thicknesses. Used substances are for example styrene-butadiene-latex, starch, polyvinyl alcohol and fillers such as kaolin, silica, titanium dioxide pigment, just to mention a few.
• the surface is to be made more repellent in character according to a present level of technique, it is possible to coat paper by separate layer of polysiloxane or siliconize the surface of the paper.
• base paper Due to the physically and chemically heterogenic nature of paper, base paper has to be modified with different manners, so that the quality of fiber material satisfies the requirements of the end application.
• the goal is to controllably adjust the capillary penetration and absorption of the solvents or other fluids such as gluey substances or pastes into the paper fibers and pores between the fibers.
• One of the most important physical methods for modification is calendering of a paper, where the fibers are packed into more compact network with the help of temperature and pressure treatment.
• printing surface is chemically improved with polymer containing pigment coating, whose thickness is typically 1-5 ⁇ m. With the aid of the pigment coating, the surface of the paper is filled up by covering the holes of the loose fiber network and the pores and the roughness by pigments.
• polymer acts as a binder, whose most important task is to bind the pigment particles together and bind the coating layer to backing paper.
• the polymer used as a binder can be in water, both in liquid or dispersed state. Structurally, the polymers can be either homopolymers or random-copolymers. As water- soluble polymers, it is typically used among others polyvinyl alcohol and carboxymethylcellulose. Dispersion polymers are synthetic latex or starch based coatings. These are among others styrene-butadiene, acrylate and vinyl acetate based latex.
• the ability of fiber material, such as paper or paper board, to bind into its surface or absorb liquid or viscous flowing substances such as glues or oily substances can be influenced with entirely novel manner by using nanotechnical approach.
• the surface of the cellulose based fiber substrates, such as surface of paper and paper board, but also as an essential factor, the inner parts of the structure are modified by bringing them into contact with small amounts of polymers.
• Polymers in this concept can be structurally homogenic homopolymers or copolymers or they can be structurally amphiphilic block polymers.
• the polymer applied in small amounts as a nanocoating on the surface of the fibers has been spread, according to the invention, on the surface of the fiber structure, and at least partly impregnated into it from a dilute aqueous solution, from an emulsion formed in water or from a dispersion formed in water.
• Homogenic polymers according to the invention are typically soluble in water or dispersible homo- or copolymers, such as advantageously polyvinyl acetate, polyvinyl alcohol or biopolymers such as lactic acid based polymers.
• Amphiphilic polymers are block polymers, which contain a hydrophilic and correspondingly a hydrophobic block. Owing to the unique structure, interaction of different blocks of the amphiphilic polymers with nonpolar or polar solvents or liquids is very different. To avoid unfavourable interactions, molecules usually form self-organized structures in solutions. Thus, amphiphiles have a long history as industrial surfactants.
• amphiphiles An important application of amphiphiles is as emulsifiers and stabilizers for emulsions.
• emulsifier the hydrophobic end of the amphiphile dissolves into hydrophobic compound and hydrophilic end reaches out to water phase.
• Block copolymers are also used in pharmacy. Self-organized structures can enclose hydrophobic drug substances, and thus add their solubility in water. Because micelles in aqueous solution can dissolve hydrophobic compounds, amphiphiles can also be used for extraction of organic molecules from water phase. Thus, the use of organic solvents can be avoided.
• the application field of amphiphilic polymers is broaden towards fibrous materials, particularly natural fiber based fiber materials such as paper and paper board, very particularly release papers used as the backing layers of labels or stickers.
• the invention provides water-soluble, colloidal or micellar form of amphiphilic block copolymers in water, which are capable of, by their fiber coating ability, even coating ability at nano level and furthest by the self-organization of amphiphilic polymers, influencing the release characteristics and adhesion characteristics of fiber material.
• the polymer is spread out on the surface of the paper as highly dilute aqueous solution, emulsion or dispersion, whereat the polymer is possible to be applied evenly as a small concentration, as water is removed during the drying stage.
• Figures 1 and 2 is presented the principle of how the amphiphilic polymers can organize on the surface of fiber material such as paper.
• the adhesion ability, capillary absorption and release ability can be influenced with amphiphilic polymers by already very small concentrations.
• the block copolymers can orientate on the surface of the fiber material or on its constituents such as individual fibers or filler particles, and through this, the hydrophobic blocks of the polymer can orientate outward form the surface and restrict the penetration of both water and solvent based liquids or viscous fluids.
• the water-soluble block of the polymer anchors the polymer on the surface of the fiber.
• Figures 1 and 2 represent diagrammicly the behaviour of the block copolymer on the surface of the paper
• Figure 3 is represented the four possible structure variations of amphiphilic polymer.
• Amphiphilic polymers are copylymers, which can be structurally linear block copolymers, graft copolymers or star copolymers. Possible structure variations are presented in Figure 3. Amphiphilicity results from the different polarities of the polymer blocks. In a limited sense, the other block of the amphiphilic copolymer, is hydrophilic, water-soluble and the other is hydrophobic, insoluble in water.
• An analogous polymer structure is such where the water- soluble polymer is modified with a hydrophobic molecule, a technique from which as an example one can mention modified polyethylene oxide (PEO), whose ends are linked by n- octadecenylsuccinic anhydride (OSA) molecules using the hydrophobic blocks.
• PEO polyethylene oxide
• OSA n- octadecenylsuccinic anhydride
• linear amphiphilic block structures are for example synthesis of macromonomers through condensation reaction, through formation of urethane, utilizing the chemistry of silicon such as with the aid of hydrosilylation reaction or utilizing living radical polymerization, just to mention a few examples.
• block copolymers composed of vinyl monomers
• block copolymers are prepared through living anionic and cationic polymerization mechanism by adding the monomers in sequence into the reaction mixture. Weakness of the method has been very low reaction temperatures and sensitivity of growing anionic chain to polar groups.
• a new method, so-called living radical polymerization, has been developed for the preparation of vinyl monomeric block copolymers.
• the reactions can be performed at room temperature in the living radical polymerization, and the method is not as sensitive to polar groups as the traditional living polymerization methods.
• Block copolymer can be structurally di- or tri-block copolymer. As mentioned above, block copolymer contains typically both water- soluble (hydrophilic) and water-unsoluble (hydrophobic) blocks.
• the hydrophilic block of the amphiphilic can be any water-soluble polymer, in which a hydrophobic block can be attached by reaction.
• a hydrophobic block can be attached by reaction.
• the hydrophilic block can be mentioned polyethylene oxide, vinyl pyrrolidone, hydroxyl ethyl methacrylate, polyvinyl alcohol in addition polyacrylic acid, and as hydrophobic blocks n-octadecenyl succinic anhydride, styrene, methyl methacrylate, vinyl acetate, polysiloxane or silicon compound and polyolefin or copolymer of monomer units typical to them.
• polyethylene oxide used as the hydrophilic block.
• the reactive groups in PEO are solely hydroxyl groups at the end of the chain, thus it is easy to prepare linear block copolymers from it.
• Other used hydrophiles in amphiphiles are among others poly(4-vinyl pyrrolidone), polymethacrylic acid and polyacrylic acid, but these polymers have to be modified into reactive by means of the chain transfer agents, or the block structure is to be prepared via living radical mechanism.
• polyalkylene oxides are possible in the implicated polymer structures.
• polyethylene oxide works as the hydrophilic block and the octadecenyl succinic anhydride as the water-insoluble block, which are connected to each other by the reaction of octadecenylsuccinic anhydride with the hydroxyl groups at the end of the PEO.
• amphiphilic block copolymer can be mentioned a form of:
• di- or tri-block copolymer formed from polysiloxane and polyalkenyl oxide, where the blocks are connected to each other by hydrosilylation reaction, and where the proportion of the polysiloxane units is advantageously 40% - 1 % and the proportion of polyalkenyl units is advantageously 60% - 99%, and where Rl and R2 are the same or lower alkyl or phenyl group, whereas the lower alkyl or phenyl group can be substituted or unsubstituted.
• this block copolymer composes of poly(di-methyl siloxane) (PDMS) and polyethylene oxide.
• Rl and R2 can also be a type of polyalkenyl oxide, partly or entirely.
• block structured copolymers prepared from polysiloxane and polyalkenyl oxide, and their preparation is described for example in publications: Haeslin & Eicke, Macromol.Chem. 185 (1984) 2625 - 2645 seka Jukarainen H., Clarson, S., Seppala, J., An Investigation of the Surface Properties and Phase Behaviour of PDMS-b-PEO Multi-block copolymers , in Silicone and Silicone Modified Materials , ACS Symp. Ser., Am. Chem.Soc. USA 1999, also Licentiate's Thesis by H. Jukarainen, University of Technology, 2000.
• Water solubility of amphiphilic polymers or their tendency to form micelles in water phase depends on the type of the block and the length.
• the water solubility level can be adjusted by molar mass of polyethene. The longer the block of polyethylene oxide, the better such an amphiphilic polymer is soluble in water.
• the block length choice and the mutual ratio of substances contributes essentially if the copolymer is soluble in water, forms micelles in it or is insoluble in water, but is dispensable in it.
• Proportions of blocks can vary in a large scale.
• the proportion of hydrophobic components is amphiphilic block copolymers is 1-85 wt-%, advantageously 5-40 wt-% and correspondingly the hydrophilic components 15-99 wt-%, advantageously 60-95 wt-%.
• Typical molar mass of the polymer is 500 - 500 OOOg/mol, advantageously 1000 - 50 000g/mol.
• the surface of the paper is not need to be filled, as in the traditional coating technique, but the polymers are applied evenly on the surface of the fibers, whereas they at least partly prevent the penetration of liquid or viscous fluids or pastes into the fiber material such as paper.
• Fiber material constituents such as on the surface of the fiber, the polymers are capable of forming even or partly even layer.
• certain roughness of the surface is, yet surprisingly according to the invention, observed to be an advantageous feature as the adjusting parameter of the release force of foreign substances, such as glue substances.
• the polymer is applied on the surface of the substrate by roll coating, curtain coating or spray coating or by some other corresponding way, typically as water dispersion or liquid, as mentioned above.
• the amount of the polymer of the surface is small and it does not block up the surface of the paper.
• Typical use amounts of amphiphilic polymers are under 3 g/m 2 , but generally on the surface of the substrate, one applies approximately 0,001 - 10 g/m , advantageously approximately 0,005 - 5 g/m , in particular approximately 0,01 - 3 g/m , of the polymer or amphiphilic block copolymer.
• the paper or paper board can be further treated for example by calendering it, always according to the application.
• a nanocoating precoated fiber materials by self-organizing amphiphilic polymers to modify the repellence of the surface so for example follow-up treatment of surface glued paper to improve its properties by applying on its surface a thin layer of polyethylene oxide modified with octadecenylsuccinic anhydride, or block or branched copolymer of polyethylene oxide and polysiloxane.
• amphiphilic block copolymer advantageously the block of polydimethyl siloxane or graft copolymer with polyethylene oxide is used as a blend component with surface glue containing essentially polyvinyl alcohol, advantageously with a proportion of 0,01 - 20wt-% from the total polymer mass to improve the release characteristics in the preparation of release paper.
• surface glue containing essentially polyvinyl alcohol
• Calendering can be performed as online calendering or offline calendering, for example by using online-softcalander or offline-supercalander.
• the square mass of the paper to be treated can be 50 - 450 g/m 2 .
• the square mass of the backing paper of paper is 30 - 250 g/m 2 , advantageously 30 - 80 g/m 2 , with paper board is 90 - 400 g/m 2 .
• Polymer compositions according to the invention can be used in very small amounts per area unit.
• a self-organized, at least partly almost monomolecular polymer nanocoating is formed on the surface of the fiber material constituents, such as on the surface of the fibers or fillers.
• the adhesion characteristics of paper are changed by means of the polymer material, in accordance with the characteristic demands of the release papers of labels.
• the roughness of surface is highly significant in adjusting the adhering of foreign substances on the surface, for example the adhering of glue substances on the surface of fiber material, particularly for example when aiming at to tailor the release force of glue labels from the release paper.
• the release force of the glue labels can be regulated within large boundaries by means of regulating the surface unevenness, thus the surface roughness, of the fiber materials treated with the polymers according to the invention. It has been observed, that by adjusting separately two parameters, the natural repellence level of the polymer and the roughness level of the surface, the release force is adjustable within a very large range.
• Advantageous combinations of the natural adhesion of the polymer and the roughness of the surface are according to the invention.
• the natural repellence of the polymer By the natural repellence of the polymer, one means the selection of polymer composition, where the polysiloxanes usually represents one of the most repellent edge points.
• the repellence of the surface can be described, for example with the contact angle of water or the surface energy values.
• the roughness of the surface one means for example unevenness of the surface by atom force microscopy, which can be typically extent of 0,1 - 50 ⁇ m, and for example in the embodiment of paper materials, it can be typically 1 - 5 ⁇ m. The more even the surface is and the smaller the values of surface roughness are, the bigger release force values are obtained.
• the fiber material according to the invention is any fiber substrate, but advantageously natural fiber mass or cellulose based fiber material such as cellulose mass, paper, paper board, paper made from recycled fiber, fabric, fiber fabric, other natural fiber masses such as flax fiber mass, plates or fabrics from synthetic fiber, or three-dimensional objects from mentioned thereof, and there can be present, in addition to fiber material, other components such as fillers. From the fillers can be mentioned minerals such as calcium carbonate and kaolin. Particularly advantageously the invention is suitable for the treatment of paper and paper board paths and sheets.
• Product fibers can be virginal fibers or recycled fibers.
• the base paper is untreated, but it is also possible to modify the surface glued paper web or sheet.
• Polyethene oxide (20 g; 2 mmol) and n-octadecenylsuccinic anhydride (5,3 g; 15,1 mmol) are placed in a laboratory bottle, where a nitrogen flow is directed. The mixture is heated at 130 0 C for 6 h.
• Product mixture is dissolved in water and extracted four times with equivalent amount of dichloromethane.
• Dichloromethane phase is collected and the solvent is removed under vacuum in a rotavapor.
• the product polymer is recovered by dissolving the evaporation residue again into dichloromethane and precipitating with diethyl ether.
• the product is separated form the solution by filtration. Finally, the product is dried under vacuum at room temperature for 8 h.
• Polyethene oxide (20 g; 3,33 mmol) and n-octadecenylsuccinic anhydride (3,5 g; 9,98 mmol) are placed in a laboratory bottle, where a nitrogen flow is directed. The mixture is heated at 130 °C for 6 h. Product mixture is dissolved in water and extracted four times with equivalent amount of dichloromethane. Dichloromethane phase is collected and the solvent is removed under vacuum in a rotavapor. The product polymer is recovered by dissolving the evaporation residue again into dichloromethane and precipitating with diethyl ether. The product is separated form the solution by filtration. Finally, the product is dried under vacuum at room temperature for 8 h.
• Polyethene oxide (20 g; 5 mmol) and n-octadecenylsuccinic anhydride (7,9 g; 22,54 mmol) are placed in a laboratory bottle, where a nitrogen flow is directed. The mixture is heated at 130 °C for 6 h. Product mixture is dissolved in water and extracted four times with equivalent amount of dichloromethane. Dichloromethane phase is collected and the solvent is removed under vacuum in a rotavapor. The product polymer is recovered by dissolving the evaporation residue again into dichloromethane and precipitating with diethyl ether. The product is separated form the solution by filtration. Finally, the product is dried under vacuum at room temperature for 8 h.
• Polyethene oxide (20 g; 10 mmol) ja n-octadecenylsuccinic anhydride (15,7 g; 44,79 mmol) are placed in a laboratory bottle, where a nitrogen flow is directed. The mixture is heated at 130 0 C for 6 h.
• Product mixture is dissolved in water and extracted four times with equivalent amount of dichloromethane.
• Dichloromethane phase is collected and the solvent is removed under vacuum in a rotavapor.
• the product polymer is recovered by dissolving the evaporation residue again into dichloromethane and precipitating with diethyl ether.
• the product is separated form the solution by filtration. Finally, the product is dried under vacuum at room temperature for 8 h.
• Solution are made from polyethene oxide monomethyl ether (20 g; 4 mmol) and propynyl chloride ( 1,1 g; 12 mmol) into dichrolomethane.
• the reaction vessel is placed in an ice bath where a nitrogen flow is directed.
• Polyethene oxide solution is added to the reaction vessel and propynyl chloride is added dropwisely into the reaction vessel during an 1 hour. Thereafter, the reaction vessel is moved at room temperature and the temperature of the reaction mixture is let to equilibrate during 18 hours.
• triethyl amine dissolved in dichloromethane is added dropwisely into the reaction mixture, until the mixture turns into alkaline.
• the solution is filtrated, half of the solvent is removed under vacuum and the macroinitiator is precipitated by cold diethyl ether.
• the macroinitiator is recovered by filtration and dried under vacuum overnight.
• Preparation of difunctional PEO macroinitiator Solution are made from polyethene oxide monomethyl ether (20 g; 2 mmol) and propynyl chloride ( 1,1 g; 12 mmol) into dichloromethane.
• the reaction vessel is placed in an ice bath where a nitrogen flow is directed.
• Polyethene oxide solution is added to the reaction vessel and propynyl chloride is added dropwisely into the reaction vessel during a 1 hour. Thereafter, the reaction vessel is moved at room temperature and the temperature of the reaction mixture is let to equilibrate during 18 hours.
• triethyl amine dissolved in dichloromethane is added dropwisely into the reaction mixture, until the mixture turns into alkaline.
• the solution is filtrated, half of the solvent is removed under vacuum and the macroinitiator is precipitated by cold diethyl ether.
• the macroinitiator is recovered by filtration and dried under vacuum overnight.
• Reaction solution was stirred with magnetic stirrer 200 rpm and dry oxygen was directed thought the solution to avoid the deactivation of the catalyst.
• Reaction xoluiton was warmed to 50°C, thereafter the catalyst (Pt(O) divinyltetramethylsiloxane complex) was added into the solution through septum.
• the amount of platinum was 30 ppm calculated from the amount of start materials.
• the polymerization was monitored by IR, until the reactions were finished, which was observed as a disappearance of the peak at 2130cm "1 . This took approximately 4 h.
• toluene was distilled from the solution by increasing temperature at 65°C and decreasing the pressure to 5 bars during 1 h.
• PDMS-PEO-PDMS - Tri-block copolymer Dehydrated alpha-vinyl ether polyethylene oxide (PEO) 5 whose molar mass is 10 OOOg/mol was weighted 4Og into a three-neck flask.
• PEO polyethylene oxide
• PDMSDIH polydimethyl siloxane
• Mn 750g/mol is weighted into same vessel and 30wt-% of distilled dry toluene. Because the amount of dimethylsilylhydride groups was in excess in the reaction, the dimethylsilyl groups were obtained in the both ends of the end product.
• Reaction solution was stirred with magnetic stirrer 200 rpm and dry oxygen was directed thought the solution to avoid the deactivation of the catalyst.
• Reaction xoluiton was warmed to 50°C, thereafter the catalyst (Pt(O) divinyltetramethylsiloxane complex) was added into the solution through septum.
• the amount of platinum was 30 ppm calculated from the amount of start materials.
• the polymerization was monitored by IR, until the reactions were finished, which was observed as a disappearance of the peak at 2130cm "1 . This took approximately 4 h.
• toluene was distilled from the solution by increasing the temperature at 65°C and decreasing the pressure to 5 bars during 1 h.
• aqueous solution emulsion or colloidal mixture or dispersion was made from the dried amphiphilic block copolymer. Coated sheet was weighted before the coating and 8h after coating. Aqueous solution was sprayed with air pressure on the surface of the paper sheet. Coating amount was adjusted with the solution volume. Wet sheet was transferred in the oven, where it was dried at 120°C for 5 min. The coating amount was determined by the weights of uncoated and coated sheets and also by the coated area.
• PEO-PDMS-block copolymers were made by using dilute aqueous solutions containing 5 wt-% of the polymer.
• a coating experiment according to example 9 was made, but in a way that the fiber material was a paper board with unevenness of 1 O ⁇ m.
• the release force was observed to be particularly low in the release test of adhesive labels, and no substance remained on the glue surface from the release paper.
• Example 15 Mixture of polysiloxane and PVA modified as polar.
• PVA polyvinyl alcohol

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Crystallography & Structural Chemistry (AREA)
• Nanotechnology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Biochemistry (AREA)
• Paper (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=35510596

Family Applications (1)

Country Status (5)

Cited By (4)

Families Citing this family (1)

Citations (6)

Family Cites Families (2)

• 2005
  • 2005-12-01 FI FI20051226A patent/FI20051226L/fi not_active Application Discontinuation
• 2006
  • 2006-11-27 GB GB0811798A patent/GB2446999B/en not_active Expired - Fee Related
  • 2006-11-27 DE DE112006003232T patent/DE112006003232T5/de not_active Withdrawn
  • 2006-11-27 WO PCT/FI2006/000388 patent/WO2007063165A1/en active Application Filing
  • 2006-11-27 CN CN2006800453166A patent/CN101341298B/zh not_active Expired - Fee Related

Patent Citations (6)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events