CN1791512A - Packaging material consisting of an at least double-layered composite material for producing containers for packing liquids - Google Patents

Packaging material consisting of an at least double-layered composite material for producing containers for packing liquids Download PDF

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Publication number
CN1791512A
CN1791512A CNA2004800134496A CN200480013449A CN1791512A CN 1791512 A CN1791512 A CN 1791512A CN A2004800134496 A CNA2004800134496 A CN A2004800134496A CN 200480013449 A CN200480013449 A CN 200480013449A CN 1791512 A CN1791512 A CN 1791512A
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CN
China
Prior art keywords
paper
cardboard
packaging material
polymer
vinyl
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Pending
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CNA2004800134496A
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Chinese (zh)
Inventor
S·钱普
R·埃特尔
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BASF SE
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BASF SE
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Publication of CN1791512A publication Critical patent/CN1791512A/en
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Classifications

    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/72—Coated paper characterised by the paper substrate
    • D21H19/76—Coated paper characterised by the paper substrate the substrate having specific absorbent properties
    • D21H19/78—Coated paper characterised by the paper substrate the substrate having specific absorbent properties being substantially impervious to the 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2377/00—Polyamides
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • D21H19/02—Metal coatings
    • D21H19/04—Metal coatings applied as foil
    • 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
    • D21H19/20—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
    • D21H19/22—Polyalkenes, e.g. polystyrene
    • 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
    • D21H19/30—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate
    • 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

Landscapes

  • Paper (AREA)

Abstract

The invention relates to packaging material which is at least composed of two layers of superposed composite material and impervious membrane and used for manufacturing vessel for packing the liquid. The composite material includes paper or paper boards which are stuck together through polymer sizing material. The invention also relates to the purpose of paper products used for producing vessels for packing the liquid, in particular for packaging beverage. The paper product is obtained through the following steps: firstly, through polymer sizing material or dispersoid of polymer sizing material and alkyl ketene dimer or the admixture of the polymer sizing material and the dispersoid, under the existence of retention aid, non essential water soluble aluminum compound and at least non essential cation polymer, paper stock composed of cellulose fibre aqueous dispersoid is felted together, secondly, water filter is performed to the paper material on the net of the paper machine, thirdly, the paper products are dried, and fourthly, plastics or metallic membrane is pressed on one surface or the upper layers of two surfaces of the paper product.

Description

Be used to make the packaging material of two laminate at least that comprise of containers for packing liquids
The present invention relates to be used for the packaging material of packing liquid, these packaging material comprise the two-layer at least laminate of a kind of sized paper or applying glue cardboard and at least a impermeable layer or paper tinsel; The invention still further relates to through mechanical applying glue and on one or both sides lamination the paper products of plastic foil or metal forming be used to make packing liquid, particularly packaged beverage purposes with container.
EP-B-0292975 discloses the alkyl ketene dimer emulsion with cation colophony sizing material and a kind of insoluble reagent (for example alum) of giving, and is used to make the purposes of packing liquid with cardboard.This cardboard is by making at the last drainage of net (wire) in the water paste of sizing material and alum adding cellulose fibre and with paper stock.
EP-A-1091043 discloses a kind of method of making the packing board that has applied, wherein with rosin size, the cellulose fibre water paste is carried out mechanical applying glue such as the synthetic size of alkyl ketene dimer and the aqueous dispersions of at least a aluminium compound, and with this water paste drainage on the net.If suitable, the aqueous dispersion of mechanical sizing material can contain dispersant, for example cationic starch, casein, cellulose derivative, polyvinyl alcohol, polyacrylamide or polyaziridine.Cardboard applies after applying glue usually.
Disclose on two sides lamination liquid-tight layer among the WO-A-02/090206 and be intended to be used for the paper products of packaged food.The alkyl ketene dimer aqueous dispersions machinery applying glue of these paper products.Based on the weight of dried paper products, the amount of alkyl ketene dimer is at least 0.25 weight %, is preferably 0.25-0.4 weight %.
Other multi-layer packaging material that basic unit is made of paper or cardboard has disclosed in for example WO-A-97/02140, WO-A-97/02181 and WO-A-98/18680.
The mechanical applying glue of using the size mixture that contains aqueous alkylketene dimer dispersions and polymeric compositions to be used for paper or cardboard is also disclosed in the prior art, referring to DE-A-3235529, WO-A-94/05855 and WO-A-96/31650.
Formerly German application 10237913.0 discloses a kind of method of packing liquid with cardboard that be used to make.In the method, by at least a retention agent and at least a cationic polymer and, a kind of water soluble aluminum compound (if suitably) exists down, with at least a mechanical sizing material the cellulose fibre water paste is carried out mechanical applying glue, and with paper stock on the net drainage make described cardboard.Described sizing material is alkyl ketene dimer, alkyl-and mixture and the product of rosin size and carboxylic acid anhydrides and the mixture of alum of alkenyl succinic anhydrides, alkyl isocyanate, rosin size and alum.
An object of the present invention is to provide the further packaging material based on paper products, wherein, these packaging material should have edge penetration and the laminate of improvement and the cohesive of paper or cardboard of special improvement.
We have found that, according to the present invention, can realize purpose of the present invention by a kind of packaging material that are used to make containers for packing liquids, these packaging material contain the two-layer at least laminate (wherein paper or cardboard are used the applying glue of polymeric compositions machinery respectively) of a kind of sized paper or applying glue cardboard and at least a impermeable layer or paper tinsel.
The invention still further relates to and be used to make packing liquid, the particularly packaged beverage purposes with the paper products of container, these paper products can obtain through the following steps:
With at least a polymeric compositions as mechanical sizing material or with polymeric compositions and aqueous alkylketene dimer dispersions or its mixture retention agent and, a kind of water soluble aluminum compound (if suitably) and, under the existence of at least a cationic polymer (if suitable), the paper stock that comprises the cellulose fibre water paste is carried out mechanical applying glue, make the paper stock drainage on the net, dry these paper products and laminated plastic film or metal forming on the one or both sides of paper products at paper machine.
Be generally used for all fibres cellulose fiber fiber of wood pulp and all annual plants for example in the paper industry, all can be used to make sized paper or applying glue cardboard.Mechanical pulp is interpreted as, expression for example grinds paper pulp, thermomechanical pulp (TMP), chemical thermo-mechanical pulp (CTMP), pressure and grinds paper pulp, semichemical wood pulp, high yield paper pulp, refiner paper pulp (RMP) and waste paper.The paper pulp that uses with bleaching or unbleached form also is suitable for.The example of these paper pulp is sulfate pulp, sulfite pulp and soda pulp.The preferred unbleached pulp that uses, described unbleached pulp is also referred to as not bleached kraft pulp.These fibers can use separately or conduct mixture each other uses.
In the mechanical applying glue of paper or cardboard,, in the process of making these materials, carry out applying glue by mechanical sizing material being added paper stock and making the online drainage of described paper stock at paper machine with sheet forming device.According to the present invention, used mechanical sizing material is a kind of polymeric compositions that contains synthetic polymer.Disclosed polymeric compositions is an aqueous polymer dispersions among the JP-A-58/115196, and it is a kind of paper sizing material and can improves strength of paper simultaneously.The polymerization in aqueous medium in the presence of starch and radical polymerization initiator makes these dispersions by for example styrene and alkyl acrylate.Used starch was cleared up earlier before polymerisation respectively or is degraded under each situation, so that it is dissolvable in water in the water.The polymer of these dispersions is styrene and the graft polymers of alkyl acrylate on starch or modified starch.
Other polymeric compositions has disclosed in EP-B-0257412 and EP-B-0267770.They are by acrylonitrile and/or methacrylonitrile and at least a monohydroxy, saturated C 3-C 8The acrylate of alcohol prepares by copolyreaction in containing the aqueous solution of degradable starch, in the presence of radical initiator by emulsion polymerisation process, and described initator is preferably hydrogen peroxide or redox initiator.The viscosities il of this degradable starch iBe 0.04-0.50dl/g.These starch are by for example natural or cation or anion-modified oxidation of starch degraded, thermal degradation, acid degradation or enzyme degraded acquisition.Advantageously use the native starch that derives from potato, wheat, corn, paddy rice or tapioca starch.Preferred enzyme degraded farina.This degradable starch in the copolyreaction in the aqueous solution, serves as emulsifying agent at for example styrene and n-butyl acrylate.Carry out containing for example at least a degradable starch of 1-25 weight % in the aqueous solution of this copolyreaction.In the such solution of 100 weight portions, polymerization is the above-mentioned monomer of 10-150 weight portion, preferred 40-100 weight portion for example.Except acrylonitrile and/or methacrylonitrile, can also use styrene in the copolyreaction, referring to WO-A-94/05855.Obtain average particulate diameter and be for example aqueous copolymer dispersion of 50-500nm, preferred 100-300nm.These polymeric dispersions are the graft polymers of used monomer on degradable starch by inference in all cases.
Styrene-based and C 3-C 8Other polymeric compositions of (methyl) alkyl acrylate copolymer has disclosed in WO02/14393.They, make by the two-stage process copolymerization in aqueous medium, in the presence of the starch and radical polymerization initiator of degraded by described monomer.
Other suitable polymers sizing material is those aqueous polymer dispersions that can make in the presence of the synthetic polymer protecting colloid.They can obtain by the mixture copolyreaction of for example following material of 2-32 part:
(a) styrene, acrylonitrile and/or methacrylonitrile,
(b) C 1-C 18The acrylate and/or the methacrylate of alcohol, and/or saturated C 2-C 4The vinyl acetate of carboxylic acid, and, if necessary,
(c) other monoene belongs to unsaturated copolymerisable monomer
Described copolyreaction is in the aqueous solution, carry out in the presence of the solution copolymerization thing of the following material copolymerization of 1 weight portion:
(1) (methyl) acrylic acid-two C 1-C 4Alkyl amino-C 2-C 4Arrcostab, if suitable, they can be protonated or quaternized,
(2) nonionic, hydrophobic ethylenically unsaturated monomer, in these monomers, if their self-polymerizations then form hydrophobic polymer, and, if necessary,
(3) monoene belongs to unsaturated C 3-C 5Carboxylic acid or their acid anhydrides, (1): (2): the mol ratio of (3) is 1: 2.5-10: 0-1.5.
At first, the solution copolymerization thing by (1) and (2) group and, (3) organize the monomer of (if suitable), copolymerization makes in the water miscible organic solvent.Suitable solvent is for example C 1-C 3Carboxylic acid, for example formic acid, acetate and propionic acid; Perhaps C 1-C 4Alcohol, for example methyl alcohol, ethanol, normal propyl alcohol or isopropyl alcohol; And ketone, for example acetone.(1) the preferred monomer that uses of group is acrylic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, the amino propyl ester of dimethylaminoethyl acrylate methyl base and acrylic acid dimethylamino propyl ester.(1) Zu monomer preferably uses with protonated or quaternised form.Suitable quaternizing agent is for example chloromethane, dimethyl suflfate and benzyl chloride.
Used (2) group monomer is nonionic, hydrophobic, alefinically unsaturated compounds, if their self-polymerizations then form hydrophobic polymer.These comprise for example C of styrene, methyl styrene, acrylic or methacrylic acid 1-C 18Arrcostab, for example methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate and isobutyl acrylate and isobutyl methacrylate, n-BMA and metering system tert-butyl acrylate.Acrylonitrile, methacrylonitrile, vinyl acetate, propionate and vinyl butyrate also are suitable for.(2) mixture of group monomer, for example the mixture of styrene and isobutyl acrylate also can be used in the copolyreaction.If suitably, the solution copolymerization thing that serves as emulsifying agent also can contain (3) group monomer with the form combination of polymerized unit, and for example monoene belongs to unsaturated C 3-C 5Carboxylic acid or their acid anhydrides, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride or itaconic anhydride.(1): (2): the mol ratio of (3) is 1: 2.5-10: 0-1.5.Like this copolymer solution dilute with water that obtains and serve as above-mentioned component (a) and (b), and (c) protecting colloid of the monomer mixture copolyreaction of (if suitable) with this form.Suitable (a) group monomer is the mixture of styrene, acrylonitrile, methacrylonitrile or styrene and acrylonitrile or styrene and methacrylonitrile.Used (b) group monomer is C 1-C 18The acrylate and/or the methacrylate of alcohol, and/or saturated C 2-C 4The vinyl acetate of carboxylic acid.This group monomer is corresponding with above-mentioned (2) group monomer.Preferred (b) group monomer that uses is butyl acrylate and butyl methacrylate, for example isobutyl acrylate, n-butyl acrylate and isobutyl methacrylate.(c) the group monomer belongs to unsaturated C for for example monoene 3-C 5Carboxylic acid, acrylamido methyl propane sulfonic acid, sodium vinyl sulfonate, vinyl imidazole, N-vinyl formamide, acrylamide, Methacrylamide and N-vinyl imidazole quinoline.Every weight portion copolymer monomer mixture of 1-32 weight portion component (a)-(c).Component (a) and monomer (b) can carry out copolymerization with any desirable ratio, and for example with 0.1: 1-1: 0.1 mol ratio is carried out copolymerization.
If necessary, can organize the performance that monomer comes modified copolymer with (c).
This class sizing material is for example being described among EP-B-0051144, EP-B-0058313 and the EP-B-0150003 to some extent.
The preferred polymeric compositions that uses be can be by the aqueous polymer dispersions of following material copolymerization acquisition:
Styrene, acrylonitrile and/or the methacrylonitrile of 20-65 weight %,
The C of 80-35 weight % 3-C 8The acrylate of saturated monohydroxy alcohol and/or methacrylate; and other monoene of 0-20 weight % belongs to unsaturated copolymerisable monomer; acrylamide for example; Methacrylamide; vinyl formamide; acrylic acid; methacrylic acid; maleic acid; itaconic acid; 2-acrylamido-2-methyl propane sulfonic acid; perhaps alkaline monomer; dimethylaminoethyl acrylate for example; dimethylaminoethyl methacrylate; the amino propyl ester of acrylic acid dimethylamino propyl ester or dimethylaminoethyl acrylate methyl; this alkalescence monomer is usually with the form of hydrochloride or to use chloromethane; dimethyl suflfate or benzyl chloride come quaternised form to use; described copolyreaction is undertaken by emulsion polymerisation process in the degradable starch aqueous solution as protecting colloid in the presence of radical initiator.The aqueous polymer dispersions of other polymeric compositions that preferably uses for obtaining by following material copolymerization:
Styrene and/or the methyl styrene of 60-90 weight %,
1,3-butadiene and/or the isoprene of 10-40 weight %, and
Other monoene of 0-20 weight % belongs to unsaturated copolymerisable monomer; for example acrylic acid, methacrylic acid, itaconic acid, acrylamide, Methacrylamide or N-vinyl pyrrolidone; described copolyreaction is undertaken by emulsion polymerisation process in the degradable starch aqueous solution as protecting colloid in the presence of radical initiator.
This polymeric compositions is cation or anionic preferably.The type that the electric charge of aqueous dispersion is combined in the comonomer in the copolymer based on the form with polymerized unit (for example; this polymeric compositions dispersion is a cationic when using alkaline unit; and combine for example acrylic acid or its salt of polymerized unit form; then causing it is anionic property), perhaps under each situation based on the electric charge of used protecting colloid.For example, use cationic starch can obtain the cationic polymer size dispersions as emulsifying agent.
For the mechanical applying glue of paper or cardboard, use based on dried paper products meter, for example the polymeric compositions (that is: 100% concentration polymer) of 0.1-2.0 weight %, preferred 0.2-0.75 weight %.
The mechanical applying glue of paper or cardboard can also carried out in the presence of the reactive sizes aqueous dispersion and in the presence of the mixture of the product of the mixture of rosin size and alum or rosin size and carboxylic acid anhydrides and alum, and described reactive sizes is for example alkyl ketene dimer, C 5-C 22Alkyl-and/or C 5-C 22Alkenyl succinic anhydride, chloro-formate and C 12-C 36Alkyl isocyanate.Except alum or with alum is used in combination, can also use other aluminum contained compound, for example disclosed polyaluminium chloride or poly-aluminium compound among the EP-B-1091043.
In reactive sizes, preferably use C 12-C 22Alkyl ketene dimer, for example stearyl dicthenone, lauryl dicthenone, palmityl dicthenone, oil base dicthenone, Shan Yu base dicthenone or its mixture.
Suitable succinyl oxide is for example decene succinyl oxide, octene succinyl oxide, dodecenyl succinic anhydride and positive hexadecene succinyl oxide.
This reactive sizes is used with the form of aqueous dispersion usually.For example, alkyl ketene dimer is scattered in the aqueous solution of cationic starch, perhaps stablizes alkylketene with nonionic or anion emulsifier.The reactive sizes dispersion that forms has cation or anionic charge or for neutral, depends on the type and the consumption of used emulsifying agent or emulsifier mixture compatible with each other.
For example, anion emulsifier can be added in the alkyl ketene dimer dispersion, described alkyl ketene dimer dispersion is emulsifiable in the water by means of cationic starch.If the electric charge of anion emulsifier has surpassed the electric charge of cationic emulsifier, then obtain alkyl diketone dimer dispersion with anionic charge.The water-based alkylketene dispersion of band anionic charge is preferably by being prepared in the aqueous solution that alkyl ketene dimer is emulsified in anion emulsifier.For example, the condensation product of naphthalene sulfonic acids and formaldehyde, sulfonated polystyrene, C 10-C 22The sodium salt of-S-alkylsurfuric acid, lignosulfonic acid, phenolsulfonic acid, naphthalene sulfonic acids or described acid, sylvite or ammonium salt can be used as anion emulsifier.The hydrolyzed copolymer of the copolymer of acrylic acid and maleic acid, acrylate homopolymer, methacrylic acid homo thing, isobutene and maleic acid and/or acrylic acid copolymer, isobutene or diisobutylene and maleic anhydride also is the emulsifying agent that is applicable to preparation anion alkyl ketene dimer dispersion.The acidic group of homopolymers or copolymer can for example partially or completely neutralize with sodium hydroxide solution, potassium hydroxide solution or ammoniacal liquor, and is used as anion emulsifier with this form.The molal weight M of homopolymers and copolymer wFor for example 1000-15000, be preferably 1500-10000.Based on reactive sizes meter to be disperseed, the consumption of emulsifying agent is for example maximum 3.5 weight %, preferred maximum 2 weight %.
Perhaps, these reactive sizes are used for the mechanical applying glue of paper products, and described paper products will be used as the base material of packaging material according to the present invention.Especially, wishing to use them when packing timber has good especially edge penetration.The consumption use that they require usually to produce the sized paper goods is for example based on the 0.1-2.0 weight % of dry cellulosic fiber, preferred 0.1-0.5 weight %.For example, per 100 parts by weight polymer sizing materials use the reactive sizes of 0-90 weight portion, preferred 50-90 weight portion.If used the mixture of polymeric compositions dispersion and the mixture of reactive sizes aqueous dispersion, then under each situation based on the polymer content meter, these mixtures contain the polymer (100% concentration) of 5-50 weight % for example, preferred 10-30 weight %.
If reactive sizes is used with polymeric compositions, then can earlier reactive sizes be added in the paper stock, can be metered into the polymeric compositions dispersion then, described reactive sizes preferred alkyl ketene dimers dispersion.But, alkyl ketene dimer dispersion and at least a polymeric compositions dispersion also can add in the paper stock simultaneously, and make the paper stock drainage with sheet forming device, perhaps will add in the paper stock, and make the paper stock drainage with sheet forming device such as the reactive sizes of at least a alkyl ketene dimer dispersion and the mixture of at least a polymeric compositions dispersion.
Certainly, by for example by means of glue pressing machine polymeric compositions being imposed on paper surface or it being sprayed onto on the paper surface, these polymeric compositions also can be used as surperficial sizing material.
The drainage of paper stock also can carry out in the presence of retention agent.Except anionic retention aids or nonionic retention agent, preferably use cationic polymer as retention agent and filter aid (drainage aid) such as polyamide.But realize significantly improving of paper machine runnability thus.Operable cationic retention aid agent is the commercially available prod of this purpose that is useful on.These are PAMCs for example, diallyl dimethyl ammoniumchloride, polyaziridine, molal weight is greater than 50000 polyamines, polyamines by grafting aziridine modification (if suitable), polyetheramides, polyvinyl imidazol, polyvinylpyrrolidone/, the polyvinyl imidazol quinoline, the polyvinyl tetrahydropyridine, poly-(dialkyl aminoalkyl vinyl ethers), poly-((methyl) propenoic acid dialkyl aminoalkyl ester) (it is protonated or quaternised form), and the polyamide-based amine that obtains by dicarboxylic acids such as adipic acid, and polyalkylene polyamine, for example also use the crosslinked diethylenetriamines of polyethylene glycol glycerin dichlorohydrin ether with the aziridine grafting according to DE-B-2434816, perhaps with the polyamide-based amine of chloropropylene oxide reaction with the generation water-soluble condensate, and the copolymer of the dialkyl amino ethyl ester of acrylamide or Methacrylamide and acrylic or methacrylic acid, the copolymer of acrylamide and propenoic acid dialkyl ammonia ethyl ester for example, described propenoic acid dialkyl ammonia ethyl ester is the form with the hydrochloric acid salify, perhaps be with the quaternised form of chloromethane.Other retention agent that is suitable for is a microparticle system, contains the cationic polymer such as trickle silica and cationic starch, perhaps contains the cationic polymer such as cation acrylamide, and bentonite.
Has at least 140 Fikentscher K value for example (is that 0.5 weight %, temperature are that 25 ℃ and pH measure in the sodium-chloride water solution of 7 5% concentration at polymer concentration) as the cationic polymer of retention agent.Based on dry cellulosic fiber meter, they preferably use with the amount of 0.01-0.3 weight %.
If suitable, except above-mentioned substance, can also in the cellulose fibre water paste, add at least a cationic polymer.The example of cationic polymer is the polyamide-based amine and/or the diallyl dimethyl ammoniumchloride of polymer, the polymer that contains vinyl guanidine unit that contains the vinyl amine unit, the polymer that contains dialkyl aminoalkyl-(methyl) acrylamide unit, polyaziridine, the grafting of usefulness aziridine.Based on dry cellulosic fiber meter, the consumption of cationic polymer for 0.001-2.0 weight % for example, be preferably 0.01-0.1 weight %.
The polymer that contains the vinyl amine unit is known, referring to US-A-4, and 421,602, US-A-5,334,287, EP-A-0216387, US-A-5,981,689, WO-A-00/63295 and US-A-6,121,409.The hydrolysis of their open chain polymer by containing N-vinyl carboxylic acid amides unit is prepared.These polymer can be for example polymerization by N-vinyl formamide, N-vinyl-N-NMF, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide and N-vinyl propionamide obtain.Described monomer polymerization separately also can be with other monomer polymerization.
With the suitable monoene of N-vinylamide copolymerization belong to unsaturated monomer be all can with the compound of its copolymerization.The example of these compounds is the vinyl acetate of the saturated carboxylic acid of 1-6 carbon atom, for example vinyl formate, vinyl acetate, propionate and vinyl butyrate; And vinyl ethers, for example C 1-C 6-alkyl vinyl ether is as methyl or ethyl vinyl ether.Other comonomer that is suitable for is C 3-C 6The ester of ethylenically unsaturated carboxylic acids, acid amides and nitrile, for example methyl acrylate, methyl methacrylate, ethyl acrylate and EMA, acrylamide and Methacrylamide and acrylonitrile and methacrylonitrile.
Other carboxylate that is suitable for is from glycol or PAG, under each situation, have only an OH base esterified, for example hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylic acid hydroxy butyl ester, hydroxy propyl methacrylate, methacrylic acid hydroxy butyl ester; And acrylic acid and molal weight are the monoesters of the PAG of 500-10000.Other comonomer that is suitable for is the ester of ethylenically unsaturated carboxylic acids and amino alcohol, for example acrylic acid dimethylamino ethyl ester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, acrylic acid diethyl amino ethyl ester, methacrylic acid diethyl amino ethyl ester, acrylic acid dimethylamino propyl ester, dimethylaminoethyl acrylate methyl base ammonia propyl ester, acrylic acid diethyl amino propyl ester, acrylic acid dimethylamino butyl ester and acrylic acid diethyl amino butyl ester.The form of the form of the salt that the alkalescence acrylate can form with the form of free alkali, with the inorganic acid of all example hydrochloric acids, sulfuric acid or nitric acid, the salt that forms with organic acid or use with quaternised form such as formic acid, acetate, propionic acid or sulfonic acid.Suitable quaternizing agent is for example dimethyl suflfate, dithyl sulfate, chloromethane, chloric ethane and benzyl chloride.
Other comonomer that is suitable for is the acid amides of ethylenically unsaturated carboxylic acids, acrylamide for example, Methacrylamide and have the N-alkyl list of the monoethylenically unsaturated carboxylic acid of 1-6 carbon atom alkyl-and two-acid amides, N methacrylamide for example, N, the N-DMAA, N-methyl acrylamide, the N-ethyl acrylamide, N-propyl group acrylamide and tert-butyl group acrylamide and alkali formula (methyl) acrylamide, for example dimethyl aminoethyl acrylamide, the dimethyl aminoethyl Methacrylamide, the diethylamino ethyl acrylamide, diethylamino ethyl-methyl acrylamide, the dimethylaminopropyl acrylamide, diethylamino propyl group acrylamide, dimethylaminopropyl Methacrylamide and diethylamino propyl methyl acid amides.
The N-vinyl imidazole of N-vinyl pyrrolidone, N-caprolactam, acrylonitrile, methacrylonitrile, N-vinyl imidazole and replacement, for example N-vinyl-glyoxal ethyline, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole and N-vinyl-2-ethyl imidazol(e) and N-vinyl imidazole quinoline N-vinyl imidazole quinoline, N-vinyl-glyoxal ethyline quinoline and N-vinyl-2-ethyl imidazol(e) quinoline for example also is suitable for use as comonomer.Except using with the form of free alkali, N-vinyl imidazole and N-vinyl imidazole quinoline also can preferably carry out this quaternization with dimethyl suflfate, dithyl sulfate, chloromethane or benzyl chloride to use with the form of inorganic acid or organic acid neutralization or with quaternised form.Poly (dially dialkyl) base ammonium halide, for example diallyldimethylammonium chloride also is suitable for.
This copolymer for example contains with the form combination of polymerized unit:
At least a N-vinylamide of-95-5mol%, preferred 90-10mol%, and
-5-95mol%, preferred 10-90mol% can belong to unsaturated monomer with other monoene of its copolymerization.These comonomers preferably do not contain acid groups.
The polymer that contains the vinyl amine unit is preferably as follows preparation: begun by the homopolymers of N-vinyl formamide or the copolymer that obtains by following material copolymerization:
-N-vinyl formamide and
-vinyl formate, vinyl acetate, propionate, acrylonitrile, N-caprolactam, N-vinyl urea, N-vinyl pyrrolidone or C 1-C 6-alkyl vinyl ether, and with this homopolymers of posthydrolysis or this copolymer, the N-vinyl formamide unit by polymerization forms the vinyl amine unit simultaneously, hydrolysis degree is for example 5-100mol%, preferred 70-100mol%.The hydrolysis of above-mentioned polymer adopts known method to be undertaken by the effect of acid, alkali or enzyme.When using acid as hydrolytic reagent, the vinyl amine unit of polymer is the form of ammonium salt, and when using basic hydrolysis, then is the free amine group form.
In most cases, the degree of homopolymers and copolymer hydrolysis is 80-95mol%.The amount of vinyl amine unit is suitable in the degree of homopolymers hydrolysis and the polymer.Under the copolymer situation of the vinyl acetate that contains the polymerized unit form, except the hydrolysis of N-vinyl formamide unit, the hydrolysis of ester group also may take place, form vinyl alcohol units.Especially, when carrying out the copolymer hydrolysis in the presence of sodium hydroxide solution, this thing happens in meeting.Chemical change can take place in acrylonitrile with the combination of polymerized unit form too in hydrolysis.For example form amide groups or carboxyl herein.Under suitable situation, contain the homopolymers of vinyl amine unit or the amidine unit that copolymer can contain maximum 20mol%, the for example reaction by formic acid and two adjacent amino groups or by the inner molecular reaction formation of an amino with adjacent amide groups of described amidine unit, described amide groups are for example with the amide groups of the N-vinyl formamide of polymerized unit form combination.The molal weight M that contains the polymer of vinyl amine unit wBe for example 500-10000000, be preferably 1000-5000000 (passing through determination of light scattering).This molal weight scope is equivalent to the K value (is that 25 ℃, polymer concentration are to measure in the sodium-chloride water solution of 5% concentration of 0.5 weight % in temperature according to H.Fikentscher) of 5-300 for example, preferred 10-250.
The polymer that contains the vinyl amine unit preferably uses with salt-free form.The polymer that contains the vinyl amine unit does not have saline solution and can for example be prepared for for example 1000-500000, the preferred daltonian suitable film of 10000-300000 by the intercepting value by means of ultrafiltration by above-mentioned saliferous polymer solution.The following aqueous solution that contains other polymer of amino and/or ammonium also can obtain with salt-free form by means of ultrafiltration.
The derivative that contains the polymer of vinyl amine unit also can be used as cationic polymer.Thus; can for example pass through amidatioon, alkylation, sulfonamides formation, urea formation, thiocarbamide formation, carbamate formation, acyl groupization, carboxy methylation, phosphonomethylization (phosphonomethylation) or the Michael addition of the amino of polymer, by the multiple suitable derivative of the polymer manufacture that contains the vinyl amine unit.Useful especially herein is uncrosslinked polyvinyl guanidine, and they can be by polymer, the preferably polyethylene base amine that contains the vinyl amine unit, with amino nitrile (R 1R 2N-CN, wherein R 1And R 2Be H, C 1-C 4Alkyl, C 3-C 6The phenyl or naphthyl that cycloalkyl, phenyl, benzyl, alkyl replace) reaction obtains, and referring to US-A-6,087,448 the 3rd hurdle the 64th walks to the 5th hurdle the 14th row.
The polymer that contains the vinyl amine unit also comprises the hydrolysis graft polymers of for example N-vinyl formamide of PAG, polyvinyl acetate, polyvinyl alcohol, polyvinyl formamide, the polysaccharide such as starch, compound sugar or monose.These graft polymers can obtain in the following manner: in the presence of at least a described grafting matrix, can also be if suitable with other copolymerisable monomer, will be for example the N-vinyl formamide in aqueous medium, carry out radical polymerization, and subsequently in a known manner the vinyl formamide unit in this grafting of hydrolysis to obtain the vinyl amine unit.
Suitable cationic polymers also can be the polymer of dialkyl aminoalkyl (methyl) acrylamide.The monomer that is applicable to this base polymer of preparation is for example dimethyl aminoethyl acrylamide, dimethyl aminoethyl Methacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl Methacrylamide, diethylamino ethyl acrylamide, diethylamino ethyl-methyl acrylamide and diethylamino propyl group acrylamide.These monomers can be used for polymerisation with the form of free alkali, with the form of inorganic or the salt that organic acid forms or with quaternised form.They can carry out Raolical polymerizable to obtain homopolymers, perhaps obtain copolymer with other copolymerisable monomer.These polymer for example contain 30mol% at least, the preferred 70mol% described alkaline monomer with the combination of polymerized unit form.
Other suitable cationic polymers is a polyaziridine, and they can be for example eliminated in the presence of the compound in acid,, prepares by the polymerisation of aziridine in the aqueous solution as catalyst with acid or lewis acid.The molal weight of polyaziridine is for example 2000000, is preferably 200-1000000.Especially preferably use the polyaziridine of molal weight as 500-750000.Under suitable situation, polyaziridine can be modified, for example alkoxylate, alkylation or amidatioon.It is synthetic that they also can carry out Michael addition or Stecker.Obtainable thus polyaziridine derivative is suitable for use as cationic polymer too.
The polyamide-based amine of aziridine grafting also is suitable for, described polyamide-based amine can by for example dicarboxylic acids and polyamines condensation reaction also subsequently the grafting aziridine obtain.Suitable polyamide-based amine by for example 4-10 carbon atom dicarboxylic acids and molecule in contain 3-10 basic nitrogen atom the polyalkylene polyamine reaction obtain.The example of dicarboxylic acids is butanedioic acid, maleic acid, adipic acid, glutaric acid, suberic acid, decanedioic acid and terephthalic acid (TPA).In the process of preparation polyamide-based amine, also can use the mixture of dicarboxylic acids, can use multiple polyalkylene polyamine equally.Suitable polyalkylene polyamine is for example diethylenetriamines, trien, tetren, dipropylenetriamine, dipropylene tetramine, two (hexa-methylene) triamine, aminopropyl ethylene diamine and two aminopropyl ethylene diamine.In order to prepare polyamide-based amine, dicarboxylic acids and polyalkylene polyamine are heated to relative higher temperature, for example be heated to 120-220 ℃, preferred 130-180 ℃ temperature.From system, remove the water that produces in the condensation course.In condensation,, also can use the lactone or the lactams of 4-8 carbon atom dicarboxylic acids if suitably.For example, every moles of dicarboxylic acids is used the polyalkylene polyamine of 0.8-1.4 mole.These polyamide-based amine aziridine grafting.This graft reaction for example such as the acid of sulfuric acid or boron trifluoride etherate or lewis acidic in the presence of, in for example carrying out under 80-100 ℃.This compounds is for example being described among the DE-B-2434816 to some extent.
Nonessential crosslinked polyamide-based amine also is suitable for and makes cationic polymer, if suitable described polyamide-based amine can also be with the other grafting of aziridine before crosslinked.The crosslinked polyamide base amine of this usefulness aziridine grafting is water miscible, and has for example daltonian mean molecule quantity M of 3000-2000000 wConventional crosslinking agent is chloropropylene oxide ether or two chloro alcohol ether (bischlorohydin ether) of for example aklylene glycol and PAG.
Other suitable cationic polymers is a PAH.This base polymer obtains by the homopolymerization of allyl amine (preferably to use the form of acid neutralization), perhaps belongs to the copolyreaction acquisition of unsaturated monomer by allyl amine and above other monoene of describing as N-vinylamide comonomer.In addition, can obtain and water-soluble cross-linked polyaziridine with free uncle and/or secondary amino group also is suitable for by the reaction of polyaziridine and crosslinking agent, described crosslinking agent is for for example having chloropropylene oxide ether or two chloro alcohol ether of the PAG of 2-100 oxirane and/or propylene oxide units.Can be for example by polyaziridine and C 1-C 22The acid amides polyaziridine that the monocarboxylic acid amidatioon obtains also is suitable for.Other cationic polymer that is suitable for is the polyaziridine of alkylating polyaziridine and alkoxide.In the alkoxide process, for example each NH unit uses 1-5 oxirane or expoxy propane in the polyaziridine.
The K value of above-mentioned cationic polymer is for example 8-300, is preferably 15-180 (being to measure in the sodium-chloride water solution under 25% of 5% concentration of 0.5 weight % at polymer concentration according to H.Fikentscher).PH is 4.5 o'clock, and their charge density preferably is at least the 4meq/g polyelectrolyte for for example 1meq/g polyelectrolyte at least.
The preferred cation polymer is the polymer that contains vinyl amine unit and polyaziridine.The example of these polymer is:
Vinyl amine homopolymers, the polyvinyl formamide of 10-100% hydrolysis, the partially or completely hydrolysate of vinyl formamide and vinyl acetate, vinyl alcohol, vinyl pyrrolidone or acrylamide copolymer has the molal weight of 3000-2000000 under each situation, and
Polyaziridine, crosslinked polyaziridine or amidated polyaziridine have the molal weight of 500-3000000 under each situation.
The polymer content of the aqueous solution is for example 1-60 weight %, is preferably 2-15 weight %, is generally 5-10 weight %.
Cardboard makes by the cellulosic fibre slurry drainage usually.The preferred kraft pulp that uses.And, use TMP and CTMP useful especially.The pH of cellulosic fibre slurry is preferably 6-8 for for example 4-8.The drainage of paper stock can carry out on paper machine in batches or carry out continuously.Can add cationic polymer, mechanical sizing material and retention agent with any selected order.Yet, preferred such step, it promptly at first is retention agent, be the cationic polymer that is preferably polyvinylamine then, be such as alkyl ketene dimer, alkyl-or at least a reactive sizes of alkenyl succinic anhydride subsequently, with the mixture of aluminium compound or these sizing materials and a kind of polymeric compositions, be added in the aqueous fiber cellulose fiber slurry.According to another specific embodiment, at first be metered at least a polymeric compositions, add retention agent then, add cationic polymer at last.
When preparing according to paper products used in the present invention, can there be other auxiliary agent that is suitable for usually, for example be used for fixative, dyestuff, bactericide and dried and/or the wet strength agent of paper.
After paper stock drainage and the paper products drying, can obtain Substance is 80-400g/m 2, be preferably 120-220g/m 2Mechanical applying glue cardboard.Laminated plastic film or metal forming, for example aluminium foil on the one or both sides of cardboard.
The suitable plastic film can be by polyethylene, polypropylene, polyamide or polyester manufacture.This film or paper tinsel can be for example by means of adhesives, and be bonding with the sized paper goods.Under this class situation, usually use the film that is coated with adhesive or paper tinsel and this laminate is suppressed.Yet, also can apply the surface of these sized paper goods with adhesive, then film or paper tinsel are placed its one or both sides, and the laminate of gained is suppressed.But, also can be directly effect by heat and pressure film or paper tinsel are stacked and placed on the cardboard to obtain laminate, cut out the suitable construction that is used to make liquid usefulness packaging material by this laminate then.These packaging material are preferred for field of food, for example are used for packaged beverage, as mineral water, fruit juice or milk, perhaps are used to make container for drink, for example cup.Under the situation of these packaging material, it is very important to have a good boundary penetration, that is, cardboard should absorb very a spot of liquid or in fact not absorb liquid.Film or paper tinsel and be better than film or paper tinsel and without the bonding force between the paper products of alkyl ketene dimer applying glue with the bonding force between the paper products of polymeric compositions applying glue.
In the following embodiments, unless context has appointment in addition, otherwise percentage all by weight.The K value is according to H.Fikentscher, and Cellulose-Chemie 13 (1932), and 58-64 and 71-74 measure in temperature is the sodium-chloride water solution of 5% concentration that 25 ℃, pH are 7, polymer concentration is 0.5 weight %.The molal weight M of polymer wPass through determination of light scattering.
Embodiment
The mensuration of edge penetration
Two sides laminated polyethylene adhesive tape at the cardboard of each manufacturing.Measure the thickness of cardboard then.Be of a size of the test-strips of 25 * 75mm by the cardboard cutting-out under each situation and under each situation, weighing then.In order to measure edge penetration, test-strips is immersed in 70 ℃ of insulations, contains in the body lotion of 30% concentration hydrogenperoxide steam generator.Test-strips stops after 10 minutes and takes out from body lotion.Absorb unnecessary hydrogen peroxide with filter paper.Test-strips is weighed once again.Calculate with kg/m by the weight that increases then 2The edge penetration of meter.
The ink flotation time
The ink flotation time (in minute) is to see through the required time of 50% test pieces according to DIN 53126 tested inks.
The Cobb value
By being kept for 60 seconds in water after, the scraps of paper carry out this test according to DIN 53132.The absorbability of water is with g/m 2Expression.
Embodiment 1 to 6
To under each situation, join in the paper stock as retention agent by the cationic starch (Solvitase BPN) based on dried paper stock 0.75%, this paper stock denseness is 10g/l and to contain 100% unbleached freedom (freeness) be the pine sulfate pulp of 20 ° of SR (Schopper-Riegler), and the pH value of mixture is adjusted into 7.Under each situation, be metered into the stearyl dicthenone (Basoplast  4118MC) of the aqueous liquid dispersion form of measuring described in the table then, and the polymeric compositions water-borne dispersions of same explanation in table 1.Fibre stuff is incorporated in drainage on the Rapid-K  then sheet forming device abundant mixing under each situation.Obtaining Substance is 150g/m 2The scraps of paper.
Use the following polymers sizing material:
Polymeric compositions A:Basoplast  250D (aqueous liquid dispersion of copolymer, as the degraded cationic starch of emulsifying agent with in the presence of as the hydrogen peroxide of initator) by the emulsion polymerization preparation of acrylonitrile and n-butyl acrylate.
Polymeric compositions B:Basoplast  265D (aqueous liquid dispersion of copolymer, as the degraded cationic starch of emulsifying agent with in the presence of as the hydrogen peroxide of initator) by the emulsion polymerization preparation of styrene and n-butyl acrylate.
Polymeric compositions C:Basoplast  PR8172 (aqueous liquid dispersion of copolymer, as the cationic starch of emulsifying agent with in the presence of as the hydrogen peroxide of initator) by the emulsion polymerization preparation of styrene and n-butyl acrylate.
Table 1
The embodiment numbering Stearyl dicthenone [%] is based on dried fiber Type The amount of polymeric compositions [%] is based on dried fiber
1 0.1 A 0.25
2 0.1 A 0.5
3 0.1 B 0.25
4 0.1 B 0.5
5 0.1 C 0.25
6 0.1 C 0.5
Then the scraps of paper being dried to moisture on the drying under steam-heated 90 ℃ is 6-10%.After the drying, measure the Cobb value of the scraps of paper.Equal lamination density is 0.918g/cm on the two sides of the scraps of paper then 2Polyethylene adhesive tape (with laminate pressurized, heated to 30 ℃).Measure the edge penetration of these three layers of laminates then.The result is as shown in table 3.
The comparative example 1 to 4
To under each situation, join in the paper stock as retention agent by the cationic starch (Solvitase BPN) based on dried paper stock 0.75%, this paper stock denseness is 10g/l and contains the pine sulfate pulp that 100% unbleached freedom is 20 ° of SR (Schopper-Riegler), and the pH value of mixture is adjusted into 7.Be metered into the stearyl dicthenone aqueous liquid dispersion (Basoplast  4118MC) of amount as shown in table 2 then.Then, fully mix the water-based fibre stuff under each situation and on Rapid-K  then sheet forming device drainage, be 150g/m to obtain Substance 2Paper products.
Table 2
The comparative example [%] stearyl dicthenone is based on dried fiber
1 0.1
2 0.2
3 0.35
4 0.60
Then the scraps of paper being dried to moisture on the drying under steam-heated 90 ℃ is 6-10%.After the drying, measure the Cobb value of the scraps of paper.Then the two sides of the scraps of paper all is bonded on the polyethylene adhesive tape and (under pressure, laminate is suppressed).Measure the edge penetration of these three layers of laminates then with respect to hydrogen peroxide.The result is as shown in table 3.
Table 3
Sample according to embodiment The Cobb of cardboard 60 seconds Edge penetration [the kg/m of laminated paper board 2] (peroxide)
1 20 10.9
2 21 10.6
3 23 6.6
4 22 4.6
5 20 10.2
6 23 11.3
Sample according to the comparative example
1 20 12.1
2 24 8.6
3 20 7.2
4 21 5.3

Claims (12)

1, a kind of packaging material comprise the two-layer at least laminate of sized paper or applying glue cardboard and at least a impermeable layer or paper tinsel, are used to make containers for packing liquids, and wherein paper or cardboard are used the polymeric compositions applying glue under each situation.
2, the packaging material of claim 1, wherein paper or cardboard are used the applying glue of polymeric compositions machinery under each situation.
3, the packaging material of claim 1, wherein paper or cardboard are used the polymeric compositions top sizing under each situation.
4, the packaging material of claim 1 wherein add applying glue to paper or cardboard in the presence of the combination of reactive sizes aqueous dispersion and/or rosin size and alum.
5, claim 1 or 2 packaging material, wherein paper or cardboard can be by adding water-based alkylketene dispersion and waterborne polymeric size dispersions and obtaining at the paper stock drainage that makes on the net of paper machine successively in paper stock.
6, claim 1 or 2 packaging material, wherein paper or cardboard can be by adding water-based alkyl ketene dimer dispersion and waterborne polymeric size dispersions and obtaining at the paper stock drainage that makes on the net of paper machine simultaneously in paper stock.
7, claim 1 or 2 packaging material, wherein paper or cardboard can be by obtaining with the size mixture applying glue that contains waterborne polymeric size dispersions and water-based alkyl ketene dimer dispersion.
8, each packaging material among the claim 1-7, wherein paper or cardboard carry out extra applying glue in the presence of cationic polymer.
9, each packaging material among the claim 1-8, wherein under each situation on the two sides of paper or cardboard all waterproof plastic foil of lamination and/or metal forming.
10, each packaging material among the claim 1-9, the wherein film of the copolymer of the copolymer of the copolymer of laminated polyethylene, polypropylene, ethene and propylene, polyester, polyvinyl alcohol, ethene and vinyl acetate, ethene and vinyl alcohol or polyamide and/or aluminium foil on the one or both sides of paper or cardboard.
11, each packaging material among the claim 1-8, wherein the Substance of paper or cardboard is 80-400g/m 2, and on the two sides equal laminated polyethylene films.
12, the purposes of paper products is used to make packing liquid, particularly packaged beverage container, and described paper products can obtain under each situation through the following steps:
(i) with at least a polymeric compositions or with dispersion or its mixture of polymeric compositions and alkyl ketene dimer water, at retention agent, and, if suitable, water soluble aluminum compound, and, if it is suitable, under the existence of at least a cationic polymer, the paper stock that contains the cellulose fibre water paste is carried out mechanical applying glue
(ii) paper machine make the paper stock drainage on the net,
(iii) dry paper products and
(iv) laminated plastic film or metal forming on the one or both sides of paper products.
CNA2004800134496A 2003-05-16 2004-05-06 Packaging material consisting of an at least double-layered composite material for producing containers for packing liquids Pending CN1791512A (en)

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DE2003122267 DE10322267A1 (en) 2003-05-16 2003-05-16 Packaging material, useful for liquids and beverages, comprises an at least two layer laminate of paper or card sized with a polymer sizing agent and at least one water-impermeable film
DE10322267.7 2003-05-16
DE102004001992.4 2004-01-13

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CN102517999A (en) * 2011-12-30 2012-06-27 珠海经济特区红塔仁恒纸业有限公司 Double-sizing preparation process for liquid packaging white cardboard
CN103158316A (en) * 2011-12-12 2013-06-19 杜邦公司 Recoverable laminated packaging material
CN103476862A (en) * 2010-12-31 2013-12-25 圣戈班艾德福斯公司 Aqueous fire retardant composition for mineral fiber mat, and resulting mats
CN103806326A (en) * 2014-02-12 2014-05-21 亚太森博（山东）浆纸有限公司 Liquid packaging body paper board and preparation method thereof
CN106592335A (en) * 2016-12-21 2017-04-26 南昌市龙然实业有限公司 Novel cation rosin sizing agent used for food packaging paper

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103476862A (en) * 2010-12-31 2013-12-25 圣戈班艾德福斯公司 Aqueous fire retardant composition for mineral fiber mat, and resulting mats
CN103476862B (en) * 2010-12-31 2016-03-23 圣戈班艾德福斯公司 For waterborne flame retardant composition and the pad obtained of the pad based on mineral fibre
CN103158316A (en) * 2011-12-12 2013-06-19 杜邦公司 Recoverable laminated packaging material
CN102517999A (en) * 2011-12-30 2012-06-27 珠海经济特区红塔仁恒纸业有限公司 Double-sizing preparation process for liquid packaging white cardboard
CN102517999B (en) * 2011-12-30 2014-08-13 珠海经济特区红塔仁恒纸业有限公司 Double-sizing preparation process for liquid packaging white cardboard
CN103806326A (en) * 2014-02-12 2014-05-21 亚太森博（山东）浆纸有限公司 Liquid packaging body paper board and preparation method thereof
CN106592335A (en) * 2016-12-21 2017-04-26 南昌市龙然实业有限公司 Novel cation rosin sizing agent used for food packaging paper

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