CN100417766C - Method of preparing paper - Google Patents
Method of preparing paper Download PDFInfo
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- CN100417766C CN100417766C CNB2005100677003A CN200510067700A CN100417766C CN 100417766 C CN100417766 C CN 100417766C CN B2005100677003 A CNB2005100677003 A CN B2005100677003A CN 200510067700 A CN200510067700 A CN 200510067700A CN 100417766 C CN100417766 C CN 100417766C
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- Prior art keywords
- polymer
- paper
- shell section
- hollow sphere
- shell
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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
- 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
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/42—Coatings with pigments characterised by the pigments at least partly organic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
Abstract
A method of preparing paper, or paperboard, using a hollow sphere polymer whose void has been created by swelling the polymer with a fixed or permanent base, incorporating the hollow sphere polymer into the paper, and drying the paper, is provided. Also provided is a paper produced by the method.
Description
The present invention relates to use its space hollow sphere polymer manufacture paper by being produced with fixed base or permanent base swollen polymer, or the method for cardboard. the invention still further relates to paper by this method preparation.
There are space or hollow emulsion polymer generally to have the multi-stage polymers of core and shell by swelling, making that having formed one or more spaces in the inside of emulsion polymer particle prepares. the hollow emulsion polymer is usually at paint vehicle, coating, printing ink, sun-screening agent, use in papermaking and several other industrial circle. in paper industry, the hollow emulsion polymer is particularly useful for making the surface of paper more level and smooth, brighter and opaquer. the additional benefits of hollow sphere polymer is to compare such as titanium dioxide with pigment or filler, their cost can reduce, therefore more worthwhile economically, and they can be given than pigment or the higher opacity of filler. in paper industry, be known that, form and dry paper, yet be coated with it with the composition that especially contains hollow emulsion polymer and pigment or filler then., the coating of paper can increase the cost of paper, thickness and/or weight. do not needing in the application of coating because of performance, this is disadvantageous, and the thickness that needs restriction paper, for example be generally used for dictionary, prescription drug treatment container insert, law is with the thickness of the paper of paper etc.
US patent No.4,594,363 disclose the method for preparing the core/sheath polymer beads that contains the space, yet comprise at high temperature with fixed base or permanent base swelling gained core/sheath polymer beads so that form the step of the dispersion of the particle that when dry, contains microvoid., this patent not have open by in the wet end of paper is processed in paper introducing they use core/sheath polymer beads to prepare the method for paper.
US patent No.6,139,961 disclose by will have core in wet end (wet-end) process of paper, around the hard polymer shell of this core with put on paper around the hollow sphere organic polymer of the flexible polymer shell of this ground floor shell and improve the intensity of paper or cardboard and the method for opacity, wherein (1) second layer shell polymeric is the 15wt% at least of the gross weight of ground floor shell polymeric and second layer shell polymeric, (2) second layer shell polymeric has and is lower than 15 ℃ glass transition temperature, (3) however this polymer with volatile alkali or fixed base or permanent base swelling., this patent does not openly have the purposes of hollow sphere polymer that glass transition temperature is higher than 25 ℃ outermost shell.
An advantage in the wet end process of paper, introducing the hollow sphere polymer be it can obtain paper as flatness, performance such as brightness and opacity, how increasing the thickness of paper need not resembling when paper is polymer-coated with hollow sphere. the applicant finds unexpectedly, the hollow sphere polymer with fixed base or permanent base swelling can be used for providing at least a of above-mentioned raising for paper, this paper is used for wherein standing exacting terms, application such as high temperature and high pressure, such as decorative laminate. the applicant further finds unexpectedly, though the hollow sphere polymer stands the wet end processing conditions, especially high temperature and/or humidity, contact subsequently even severeer condition, for example decorative laminate processing, when when pigment in wet end is used in combination, wherein in wet end, use pigment to be lower than, but the cost of the cost that is reached without the hollow sphere polymer, the hollow sphere polymer still can be given the decorative laminate product with improved opacity.
First aspect of the present invention is the method for preparing paper or cardboard, comprise the following steps: that (a) provides via (i), (ii) and the (iii) hollow sphere polymer of preparation: (i) belong to unsaturated monomer and form core section polymer by at least a monoene that contains acid functional group of polymerization, (ii) be polymerized to less a kind of shell section monomer system by emulsion in the presence of described core section polymer, with the described core section of at least a shell section polymeric encapsulate polymer, wherein said shell section polymer can permeate fixed base or permanent base, and wherein said shell section polymer has and is higher than 25 ℃ glass transition temperature; (iii) allow gained multi-stage polymeric composition granule contact with fixed base or permanent base, wherein (1) described shell section polymer comprises at least 1% acid functional monomers, or (2) described contact is carried out in the presence of solvent; (b) in the wet end of described paper or cardboard forms, in described paper or cardboard, introduce the composition that comprises described hollow sphere polymer; (c) dry described paper or cardboard.
Second aspect of the present invention is the method for preparing decorative laminate, comprise the following steps: that (a) provides via (i), (ii) and the (iii) hollow sphere polymer of preparation: (i) belong to unsaturated monomer and form core section polymer by at least a monoene that contains acid functional group of polymerization, (ii) be polymerized to less a kind of shell section monomer system by emulsion in the presence of described core section polymer, with the described core section of at least a shell section polymeric encapsulate polymer, wherein said shell section polymer can permeate fixed base or permanent base, and wherein said shell section polymer has and is higher than 25 ℃ glass transition temperature; (iii) allow gained multi-stage polymeric composition granule contact with fixed base or permanent base, wherein (1) described shell section polymer comprises at least 1% acid functional monomers, or (2) described contact is carried out in the presence of solvent; (b) allow described decorative laminate contact with the composition that contains described hollow sphere polymer and at least a pigment, wherein said contact comprises that (1) is coated with described decorative laminate with described composition, or (2) introduce described composition in described decorative laminate in the wet end of described decorative laminate forms; (c) dry described decorative laminate.
Second aspect of the present invention be by this first or the formed paper of method of second aspect.
Method of the present invention relates to the preparation of the paper of the hollow sphere polymer that has therein the fixed base introduced or permanent base swelling. and the first step of this method provides the hollow sphere polymer, it has the multi-stage polymers of the core section of being sealed by the shell section by formation, then by allowing it and fixed base or permanent base contact the swelling multi-stage polymers to prepare to form the hollow sphere polymer. this class hollow sphere polymer is well-known in the art, and can be purchased.
Core section polymer is to belong to the formed emulsion polymer of unsaturated monomer by at least a monoene that contains acid functional group of polymerization. this core section polymer is by containing the emulsion homopolymerization of sour monomer, or preparing with at least a copolymerization of monomer that other contains acid by this monomer that contains acid. the suitable monoene that contains acid functional group that can be used for preparing core section polymer belongs to unsaturated monomer and comprises the monomer that for example contains at least one hydroxy-acid group, comprise acrylic acid, methacrylic acid, acryloxy propionic, (methyl) acryloxy propionic, itaconic acid, aconitic acid, maleic acid or acid anhydrides, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate; It is also contemplated that the oligomer that uses terminal unsaturation to contain acid, for example at US patent No.5,710,227 and 6,046,278 and EP 1010706 in the instruction those, comprise comb shape/grafting, block and mix block oligomers. in disclosure thing, at another term such as acrylate, the use of the term " (methyl) " before acrylonitrile or the acrylamide is meant acrylate respectively, acrylonitrile, or acrylamide and methacrylate, methacrylonitrile and Methacrylamide. acrylic acid and methacrylic acid are preferred.
Generally, contain at least approximately 5wt%, yet the preferred core copolymer of the acid monomers unit of 10wt% at least has practical swellable for the present invention., because the hydrophobicity of some comonomer, can have the situation that this copolymer wherein need be higher or lower than the monomer that contains acid of 5wt%. as mentioned above, core section polymer can form by the homopolymerization of monomer that contains acid. therefore, the present invention includes the core of the monomer that contains acid that contains 100% emulsion polymerisation. and the preferred maximum of acidiferous monomer is about 70wt%. of total core section monomer
In preferred embodiments, the monomer and one or more nonionic monoene that contain acid belong to the unsaturated monomer copolymerization. in one embodiment, the 5-100wt% of core section polymer by allowing based on the weight of core section polymer, preferred 20-60wt% and more preferably 30-50wt% at least a contain the ethylenically unsaturated monomer of acid functional group and belong to the unsaturated monomer copolymerization and form based at least a nonionic monoene of the 0-95wt% of the weight of core section polymer. the suitable nonionic monoene that is used to prepare core section polymer belongs to unsaturated monomer and comprises styrene, α-Jia Jibenyixi, p-methylstyrene, t-butyl styrene, vinyltoluene, ethene, vinyl acetate, vinyl chloride, vinylidene chloride, (methyl) acrylonitrile, (methyl) acrylamide, (methyl) acrylic acid (C
1-C
20) Arrcostab or (C
3-C
20) alkenyl ester, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid Lauryl Ester, (methyl) acrylic acid oil base ester, (methyl) acrylic acid palmityl ester, (methyl) stearyl acrylate base ester etc.
Core section polymer can randomly contain the 20wt% that is lower than based on the gross weight of core, and the polyenoid of preferred 0.1-3wt% belongs to unsaturated monomer, and wherein this consumption is general belongs to the unsaturated consumption that contains sour monomer with monoene and roughly be directly proportional; In other words, when monoene belonged to the unsaturated relative quantity that contains the monomer of acid and increases, suitable was to increase the consumption that polyenoid belongs to unsaturated monomer. as selection, the core polymer can contain the butadiene based on the 0.1-60wt% of the gross weight of core polymer.
But the polyenoid that is fit to belongs to the comonomer that unsaturated monomer comprises the ethenylidene (vinylidene) that contains at least two addition polymerizations, and be the α that contains the polyalcohol of 2-6 ester group, β-olefinic unsaturated monocarboxylic ester. these comonomers comprise aklylene glycol diacrylate and dimethylacrylate, glycol diacrylate for example, ethylene glycol dimethacrylate, 1, the 3-butanediol diacrylate, 1, the 4-butanediol diacrylate, propylene glycol diacrylate, and triethylene glycol dimethacrylate; 1,3-glycerine dimethylacrylate; 1,1,1-trimethylolpropane dimethylacrylate; 1,1,1-trimethylolethane diacrylate; Pentaerythritol acrylate trimethyl; 1,2,6-hexane triacrylate; Sorbierite pentamethyl acrylate; Methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, divinylbenzene, metering system vinyl acetate, Vinyl crotonate, vinyl acrylate, vinylacetylene, trivinylbenzene, triallyl cyanurate, divinylacetylene, divinyl ethane, divinyl sulfide, divinyl ether, divinylsulfone, diallyl cyanamide, ethylene glycol bisthioglycolate vinethene, diallyl phthalate, the divinyl dimethylsilane, glycerine trivinyl ether, adipic acid divinyl ester; (methyl) acrylic acid dicyclopentenyl ester; Two cyclopentene oxygen base (methyl) acrylate; The beta-unsaturated esters of glycol monomethyl dicyclopentenyl ether; Have the monocarboxylic acid of terminal ethylenic unsaturated bond and the allyl ester of dicarboxylic acids, comprise (methyl) allyl acrylate, diallyl maleate, diallyl fumarate, itaconic acid diallyl etc.
The shell section of hollow sphere polymer of the present invention preferably has and is moderate to high glass transition temperature (Tg) relatively. preferably, outermost shell section polymer Tg is higher than 25 ℃, more preferably is higher than 50 ℃, also more preferably is higher than 70 ℃, most preferably be higher than 90 ℃, calculate (T.G.Fox, Bull.Am.Physics Soc., the 1st volume by the Fox equation, the 3rd distribution, 123 pages (1956)). that is to say, for the Tg of the copolymer that calculates monomer M 1 and M2
1/Tg (calc.)=w (M1)/Tg (M1)+w (M2)/Tg (M2), wherein
Tg (calc.) is the calculating glass transition temperature of copolymer
W (M1) is the weight fraction of the monomer M 1 in copolymer
W (M2) is the weight fraction of the monomer M 2 in copolymer
Tg (M1) is the glass transition temperature of the homopolymers of M1
Tg (M2) is the glass transition temperature of the homopolymers of M2,
All temperature are by a ° K.
Shell section polymer is the product of emulsion polymerisation shell section monomer system in the presence of core section polymer. employed monomer and their relative scales in shell section polymer should make shell section polymer allow the infiltration of fixed base or permanent base. preferably, yet shell section monomer system can all be an acrylic compounds., in particularly preferred embodiments, shell section polymer contains the butyl methacrylate as copolymerization units, methyl methacrylate and about 1 arrives the methacrylic acid of about 10wt%.
As indicated above, in one embodiment of the invention, core section polymer contains and has containing the ethylenically unsaturated monomer of acid functional group and belonging to the copolymer of unsaturated monomer based at least a nonionic monoene of the 0-95wt% of the weight of core section polymer based on the 5-100wt% of the weight of core section polymer at least a as copolymerization units; And shell section polymer forms by belonging to unsaturated monomer based on about 90 to about 99.9wt% at least a nonionic monoene of the gross weight of shell section polymer and belonging to polymerization of unsaturated monomers based on about 0.1 to about 10wt% acid-functionalized monoene of the gross weight of shell section polymer. in this embodiment, when the granularity of core section polymer when being about 130nm to about 2.0 μ m, acid-functionalized monoene belongs to unsaturated monomer and preferably joins shell section monomer combined feed in feeding 100%, more preferably preceding 50% charging, also more preferably preceding 25% charging, in the polymerization of the shell section polymer during most preferably preceding 10% charging, gross weight in shell section monomer feed is a benchmark. when the granularity of shell section polymer during less than about 130nm, acid-functionalized monoene belongs to unsaturated monomer and preferably joins shell section monomer combined feed in feeding 50%, in the polymerization of the shell section polymer when more preferably preceding 25% charging and most preferably preceding 10% charging, be benchmark in the gross weight of shell section monomer feed.
The hollow sphere polymeric system must (1) contains and has the shell section monomer system of 1wt% acid functional monomers at least, and remainder can be that the nonionic monoene belongs to unsaturated comonomer, such as above for core section polymer described those; Or (2) are included in swelling hollow sphere polymer under the existence of solvent. when not using solvent, acid functional monomers is 5-10wt% in the preferred amounts of the monomer system that is used for preparing shell section polymer; When using solvent, be about 1-2wt%.
When using solvent, it helps shell alkali or the permanent base infiltration that is fixed. by 100 weight portion hollow sphere polymer, the suitable amount of solvent is the 1-100 weight portion, preferred 5-10 weight portion. but suitable solvent is any of plasticising shell, for example, hexanol, ethanol, isobutyric acid 3-hydroxyl-2,2,4-tri-methyl-amyl ester, toluene, the mixture of solvent etc. this solvent can be before adding alkali, add afterwards or simultaneously. and in some cases, shell section monomer system itself can be as the solvent of shell section polymer.
Especially, within the scope of the invention be: the shell section polymer of sealing core section polymer fully; Basically, but not exclusively seal the shell section polymer of core section polymer; Swellable is with surface and the inside of particle, the i.e. polymer of the particle at least one hole that communicates between core or the space that is provided at particle; Polymer beads with a plurality of cores; Multi-stage polymers, its SMIS polymer are the precursors that contains the core polymer of acid functional group of the present invention, subsequently, no matter before shell polymeric forms, during or afterwards, by according to US patent Nos.5,041,464; 5,157,084; With 5,216, the mode of 044 instruction is converted into the core polymer that contains acid functional group of the present invention such as the hydrolysis of core polymer, and during hydrolysis or afterwards, this core polymer contacts with fixed base or permanent base.
In one embodiment of the invention, with shell section crosslinked polymer. the total mole number in the monomer that uses in the hollow sphere polymer is benchmark, crosslinked level is 2mol% at least preferably, more preferably crosslinked can by use one or more polyenoid belong to unsaturated monomer obtain of 5mol%. in shell at least. the polyenoid that is fit to belong to unsaturated monomer comprise above for core section polymer described those. in addition, the crosslinked of shell section polymer can obtain by using one or more multiple functionalized monomers, so that provide crosslinked after the polymerization of shell. multiple functionalized monomer contain functional group that at least one can the vinyl copolymerization and at least one can with the functional group of the reactive molecule reaction that is fit to. suitable reactive molecule comprises for example amine, two amines, amino acids and aminoalkyl trialkoxy silane; Optional other reactive molecule of adding subsequently: aldehydes (such as formaldehyde), twain-aldehyde compound (such as glutaraldehyde), hydrazine class and two hydrazine classes (such as butanedioic acid two hydrazines), crosslinked sol-gel after the formation polymerization.
The example of crosslinked multiple functionalized monomer is not with restrictedly in European patent application EP 1092421 illustrated after being used for suitable functional group and reactive molecule crosslinked after the polymerization of shell section polymer and being suitable for polymerization.
The multi-stage polymeric composition granule that contains core section and shell section polymer prepares by the order emulsion polymerisation process, these methods are known in the art, for example be described in U.S. Patent No. 4,594, in 363. so-called " order emulsion polymerisation " here be meant the polymer stage that the homopolymers in a stage of polymer or copolymer formerly form by emulsion polymerisation by emulsion polymerisation process in aqueous medium dispersed polymeres particle in the presence of prepare, make the deposition of emulsion polymeric product of one or more the follow-up monomer addition in the medium of the discrete particles by being incorporated into the emulsion polymer that contains previous formation, the size of the previous emulsion polymer that forms increases. and each section of hollow sphere polymer can prepare in single stage of sequential polymerization or step, perhaps can prepare in a plurality of steps according to the order of sequence.
In order emulsion polymerisation involved in the present invention, term " seed " polymer is used for representing the aqueous emulsion polymers dispersion, it can be the dispersion that contains the polymer stage that at first forms, perhaps it can be the emulsion polymer dispersion that obtains at the end of any follow-up phase except the terminal stage of sequential polymerization. therefore, the core section polymer itself of planning to seal with one or more follow-up emulsion polymerisation stages can be called as the seed polymer that is used for next stage. and same, seed polymer can be used for forming the nuclear that forms core section polymer thereon.
Water-soluble radical initiator can use in aqueous emulsion polymerization. and the water-soluble radical initiator that is fit to comprises hydrogen peroxide; Tert-butyl peroxide; Alkali metal persulphate is such as sodium peroxydisulfate, potassium and lithium; Ammonium persulfate; Mixture with these initators and reductant. reductant comprises: sulphite, such as the alkali metal pyrosulfite, bisulfites, and sulfoxylate; Sodium formaldehyde sulphoxylate; With reducing sugar such as ascorbic acid and arabo-ascorbic acid. by the gross weight of monomer, the amount of initator is 0.01-3wt% preferably, in redox system, the amount of reductant can be in about 10 ℃ to 100 ℃ scope based on the 0.01-3wt%. temperature of the total amount of monomer preferably. under the situation of persulfate system, temperature is preferably in 60-90 ℃ scope. in redox system, and preferably 30-70 ℃ of temperature.The type of initator and amount can be identical or different in each section of multi-stage polymeric.
One or more nonionics or anion emulsifier or surfactant can use separately or together. and the example of the nonionic emulsifier that is fit to comprises that uncle's Octylphenoxy ethyl gathers (39)-ethoxy ethanol, dodecyloxy gathers (10) ethoxy ethanol, Nonylphenoxy ethyl-poly-(40) ethoxy ethanol, the Macrogol 2000 monoleate, ethoxylated castor oil, fluorinated alkyl esters and alcoxylates, polyethylene glycol oxide (20) Arlacel-20, sucrose list cocounut oil acid esters, two (2-butyl) phenoxy group gathers (20) ethoxy ethanol, hydroxyethylcellulose butyl polyacrylate graft copolymer, poly-(ethylene oxide) poly-(butyl acrylate) block copolymer, the block copolymer of expoxy propane and oxirane, with 2 of the oxirane ethoxylation of 30mol, 4,7,9-tetramethyl-5-decine-4, the 7-glycol, N-polyethylene glycol oxide (20) lauramide, N-lauryl-N-polyethylene glycol oxide (3) amine and poly-(10) ethylene glycol dodecyl thioether. the example of suitable anion emulsifier comprises NaLS, neopelex, potassium stearate, sodium dioctyl sulfosuccinate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, the Nonylphenoxy ethyl gathers (1) ethoxyethyl group ammonium sulfate, Sodium styrene sulfonate, dodecyl allyl sulfosuccinate sodium, linseed oil fatty acid, the sodium salt of the phosphate of ethoxylated nonylphenol or ammonium salt, Octoxinol (octoxynol)-3-sodium sulfonate, the cocoyl sodium sarcosinate, 1-alkoxyl-2-hydroxypropyl azochlorosulfonate acid sodium, alpha-olefin (C
14-C
16) sodium sulfonate, the sulfate of hydroxyl alkanol, N-(1,2-dicarboxyl ethyl)-N-octadecyl sulfo group-succinamic acid four sodium, N-octadecyl sulfosuccinamic acid disodium, alkyl amido polyethoxy disodium sulfosuccinate, the sodium salt of poly-(39) the ethoxyethyl group sulfuric acid of the ethoxylated nonylphenol Carbenoxolone Sodium of sulfosuccinic acid and uncle's Octylphenoxy ethyoxyl. these one or more surfactants generally use with the level of 0-3%, weight in multi-stage polymers is benchmark. these one or more surfactants can add before adding any monomer addition and/or in the interpolation process in monomer addition. and are being used to form in some monomer/emulsifier system of shell, forming glue or coagulative tendentiousness in reaction medium can reduce or prevent by adding about emulsifying agent of 0.05 to about 2.0wt% based on the gross weight of shell polymeric, can not damage the deposition of the polymer that forms on the slug particle of formation formerly.
Gross weight by the core polymer is a benchmark, the amount of emulsifying agent can be 0 (using therein under the situation of persulfate initiator) to 3wt%. by carry out emulsion polymerisation when keeping low-level emulsifying agent, the follow-up phase that polymer forms with the polymer deposition of up-to-date formation on the existing dispersed polymeres particle that obtains by previous step or stage. as rule, the amount of emulsifying agent should remain below the amount corresponding to the critical micelle concentration of specific monomer system, but this boundary is preferred and has formed unimodal product simultaneously, have been found that, in some system, can be just over the critical micelle concentration of emulsifying agent, can not form harmful or excessive dispersion micelle or particle. this is used for the number at each polymerization stage control micella, make that it is lower that the concentration of emulsifying agent keeps on the dispersion micelle or particle that the polymer deposition of formation formed in the stage formerly afterwards in each stage.
The viscosity-average molecular weight of the polymer that forms in set stage can be 100,000 is (or lower, if use chain-transferring agent) to millions of molecular weight. when use in the preparation core belongs to unsaturated monomer based on the above-mentioned polyenoid of the 0.1-20wt% of the weight of monomer, no matter whether take place crosslinked, molecular weight increases. when multi-stage polymers is handled with the sweller of core, if polyenoid belongs to the tendentiousness that the use of unsaturated monomer has reduced the core polymer dissolution. wish to form the latter half that has in this scope, such as 500,000 to being low to moderate about 20, the core of 000 molecular weight, usually the most practical is belongs to unsaturated monomer and uses chain-transferring agent (such as 0.05-2% or more) to substitute and do like this by the cancellation polyenoid, example is an alkyl hydrosulfide, such as sec-butyl mercaptan.
The amount that is deposited as the polymer of shell polymeric generally should reach provides 70nm to 4.5 μ m under non-swelling condition, preferred 100nm is to 3.5 μ m, more preferably 200nm is to the degree of the overall dimension of the multi-stage polymeric composition granule of 2.0 μ m, no matter shell polymeric forms in the single stage still is a plurality of stages. and in order at utmost to reduce the dry density of end product, preferred only deposition is sealed the shell polymeric of the required amount of core fully.
When particle is handled with fixed base that can the swelling core or permanent base, the multi-stage polymers that contains core and shell section polymer is by swelling, forming the hollow sphere polymer. the swelling of core or the external peripheral zone ground that can comprise core of expanding merge in the hole in interior week of shell and shell and whole particle part generally enlarge or expand. and suitable sweller is to permeate those of shell and swelling core in the presence of multistage emulsion polymer. and what is called " fixed base or permanent base " is meant non-volatile hard base here, such as metal hydroxides, NaOH for example, potassium hydroxide, lithium hydroxide, strontium hydroxide, barium hydroxide. preferably NaOH and potassium hydroxide. fixed base or permanent base are different from room temperature or more or less are evaporated from emulsion when drying and have " volatile alkali " of pKb＜7 (in 25 ℃ water), such as ammonia, ammonium hydroxide, amine, the salt of weak acid.Can add solvent, ethanol for example, hexanol, octanol,
Solvent and in US patent 4,5 94, those described in 363 are to help the infiltration of fixed base or permanent base.
In one embodiment of the invention, the composition that will contain the hollow sphere polymer in the wet end forming process of paper or cardboard is incorporated in paper or the cardboard. and so-called " wet end " is meant the part of paper or cardboard processing here, during this period, use technology well known in the art, main cellulosic pulp fiber slurry is configured as wet web on paper machine. the hollow sphere polymer joined in the slurry, and mix with this slurry, be configured as then and contain or introduced the paper of hollow sphere polymer or the wet web of cardboard. dry then paper or cardboard. when the hollow sphere polymer beads in paper or cardboard is dry to small part, they have produced advantageous property, such as bulk density, brightness and opacity are given the polymer beads that the space is arranged of paper or cardboard.
Be well known in the art and use the hollow sphere polymer to substitute or expand pigment, so that reduce the cost of final products. at the hollow sphere polymer not under the situation that pigment uses, yet can obtain favourable performance such as brightness and opacity., in certain embodiments of the invention, the hollow sphere polymer is used in combination with pigment. and pigment adds in the wet end process of paper or cardboard with the hollow sphere polymer. can use any pigment, comprise for example calcium carbonate, talcum, clay, titanium dioxide etc. preferably, the hollow sphere polymer is used for the expensive pigment of increment, such as titanium dioxide. therefore, this pigment is incorporated in paper or the cardboard with the hollow sphere polymer.
Method of the present invention can be used to prepare the paper of any kind. in one embodiment of the invention, the paper that contains the hollow sphere polymer approaches, treat the container insert such as dictionary with paper, prescription drug, law is with paper etc. and in this embodiment, paper generally has the thickness of about 0.5 Mill to about 2 Mills.
As mentioned above, the hollow sphere polymer is not at present by introducing in decorative laminate or using in the manufacture process at decorative laminate in coating on the decorative laminate. and so-called " decorative laminate " is meant that class paper that is generally used for making decorative laminate here. usually, decorative laminate with wear-resisting synthetic resin lamination before print and/or embossing, to form decorative laminate. in one embodiment of the invention, the paper that contains the hollow sphere polymer is typically under severe condition, such as high temperature, carry out that class paper of following process under high pressure and/or the high humility, decorative laminate for example. in this embodiment of the present invention, as mentioned above, the hollow sphere polymer can be incorporated in the decorative laminate in the wet end process of paper. and in addition, the hollow sphere polymer can be coated on the decorative laminate of established optionally drying.
Following examples illustrate concrete aspect of the present invention and particular, yet they should not be considered to restrictive.
Embodiment 1: the preparation of hollow sphere polymer
Give 5L round-bottomed flask assembling paddle agitator, thermometer, nitrogen inlet and reflux condenser. add the sodium peroxydisulfate of the 2.5g in the deionized water be dissolved in 30g to the deionized water that under nitrogen atmosphere, in flask, is heated to 90 ℃ 1780g. after this immediately with 275g in U.S. Patent No. 5,494, the core of preparation adds in this still among 971 the embodiment 0-(a), reaction temperature is corresponding to be reduced to 80 ℃. will contain the deionized water of 70g with 25 minutes times, the Siponate DS-4 of 1g, acrylic acid monomer emulsions of the styrene of 80g and 12g joins in the still. when first feed finishes, the deionized water that will contain 210g through 75 minutes times, the Siponate DS-4 of 10g, the styrene of 781g, 1.52g linseed oil fatty acid and second monomer emulsions of the allyl methacrylate of 3.2g join in this still. with these chargings, the solution of sodium peroxydisulfate in the deionized water of 150g of 1.4g is fed in this still jointly. reaction mixture temperature is elevated to 90 ℃. when second monomer emulsions and co-fed interpolation are intact, the mixture of the versene (veresene) of 1.5% ferrous sulfate of 5g and 5g is joined in the still. simultaneously, this still is cooled to 85 ℃. when reaching 85 ℃, will be by the deionized water of 70g, 21.9g Siponate DS-4, the 3rd monomer emulsions that the styrene of 170g and the TEMPO of 2.5g form joins in this still. add 3.3% heat (85 ℃) solution of the NaOH of 500g after this.After 85 ℃ keep 20 minutes down, add the solution of tBHP in the deionized water of 25g of 4.14g, afterwards immediately with the arabo-ascorbic acid that was total to the 2.57g of feeding in the 85g deionized water in 20 minutes. with the end product cool to room temperature, obtain the 1100nm particle of 26% total solid, had 55% voidage.
Embodiment 2: the wet end of hollow sphere polymer is introduced
The hollow sphere polymer of embodiment 1 and refining wood pulp are mixed, the blend of the ratio with 10: 90 hollow sphere pigment and wood pulp is provided, this blend under agitation is diluted to 0.2% solid dispersions, form pattern product with CTP (Centre Technique de Papier) Retention Former. like this pattern product of Xing Chenging in 95 ℃ baking oven under 50% relative humidity drying 10 minutes. this dry run is descended relative humidity (20-80%) and drying time (2-20 minute) repetition in the temperature (50-90 ℃) of certain limit.
Gained paper has than higher opacity of the paper of the hollow sphere polymer that does not contain hard alkali swelling and higher bulk density (more low-density paper).
Embodiment 3: the wet end of hollow sphere polymer is introduced
With the hollow sphere polymer of embodiment 1, refining wood pulp and TiO
2Slurry mixes, and provides to have 20/60/20 hollow sphere pigment and wood pulp and TiO
2The blend of ratio (by dry weight basis). this blend under agitation is diluted to 0.2% solid dispersions, forms the pattern product with CTP (CentreTechnique de Papier) Retention Former.
The pattern product of Xing Chenging are in 95 ℃ baking oven under 50% relative humidity dry 10 minutes like this. and this dry run is in the temperature (50-90 ℃) of certain limit, and relative humidity (20-80%) and drying time (2-20 minute) be repetition down.
Gained paper has than higher opacity of the paper of the hollow sphere polymer that does not contain hard alkali swelling and higher bulk density (more low-density paper).
Claims (8)
1. prepare the method for paper or cardboard, comprise the following steps:
(a) provide via (i), (ii) and (iii) the hollow sphere polymer of preparation:
(i) belong to unsaturated monomer by at least a monoene that contains acid functional group of polymerization and form core section polymer,
(ii) be polymerized to less a kind of shell section monomer system by emulsion in the presence of described core section polymer, with the described core section of at least a shell section polymeric encapsulate polymer,
Wherein said shell section polymer can permeate fixed base or permanent base,
Wherein said shell section polymer has and is higher than 25 ℃ glass transition temperature;
(iii) allow gained multi-stage polymeric composition granule contact with fixed base or permanent base,
Wherein (1) described shell section polymer comprises at least 1% acid functional monomers, or (2) described contact is carried out in the presence of solvent;
(b) in the wet end of described paper or cardboard forms, in described paper or cardboard, introduce the composition that comprises described hollow sphere polymer; With
(c) dry described paper or cardboard.
2. according to the process of claim 1 wherein that described core section polymer forms by allowing 5 to 100wt% the described monoene that contains acid functional group based on the gross weight of core section polymer belong to unsaturated monomer and to belong to polymerization of unsaturated monomers based on 0 to 95wt% at least a nonionic monoene of the gross weight of core section polymer;
Wherein said shell section polymer forms by allowing 90 to 99.9wt% at least a nonionic monoene based on the gross weight of shell section polymer belong to unsaturated monomer and to belong to polymerization of unsaturated monomers based on 0.1 to 10wt% acid-functionalized monoene of the gross weight of shell section polymer.
3. the process of claim 1 wherein that described shell section polymer carries out crosslinked.
4. the process of claim 1 wherein that described paper has the thickness of 0.5 Mill to 2 Mills.
5. according to the process of claim 1 wherein that the composition of described introducing further comprises at least a pigment.
6. the paper that forms of each the method by claim 1-5.
7. prepare the method for decorative laminate, comprise the following steps:
(a) provide via (i), (ii) and (iii) the hollow sphere polymer of preparation:
(i) belong to unsaturated monomer by at least a monoene that contains acid functional group of polymerization and form core section polymer,
(ii) be polymerized to less a kind of bright section monomer system by emulsion in the presence of described core section polymer, with the described core section of at least a shell section polymeric encapsulate polymer,
Wherein said shell section polymer can permeate fixed base or permanent base,
Wherein said shell section polymer has and is higher than 25 ℃ glass transition temperature;
(iii) allow gained multi-stage polymeric composition granule contact with fixed base or permanent base,
Wherein (1) described shell section polymer comprises at least 1% acid functional monomers, or (2) described contact is carried out in the presence of solvent;
(b) allow described decorative laminate contact with the composition that contains described hollow sphere polymer and at least a pigment,
Wherein said contact comprises that (1) is coated with described decorative laminate with described composition, or (2) introduce described composition in described decorative laminate in the wet end of described decorative laminate forms; With
(c) dry described decorative laminate.
8. pass through the decorative laminate of the method formation of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04291069 | 2004-04-23 | ||
| EP04291069.5 | 2004-04-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1690307A CN1690307A (en) | 2005-11-02 |
| CN100417766C true CN100417766C (en) | 2008-09-10 |
Family
ID=34931051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100677003A Expired - Fee Related CN100417766C (en) | 2004-04-23 | 2005-04-22 | Method of preparing paper |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20050236125A1 (en) |
| CN (1) | CN100417766C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102704313B (en) * | 2012-06-08 | 2015-06-10 | 方汉佐 | High-speed reverse-net multi-roller drying special type papermaking technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594363A (en) * | 1985-01-11 | 1986-06-10 | Rohm And Haas Company | Production of core-sheath polymer particles containing voids, resulting product and use |
| EP0419206A1 (en) * | 1989-09-21 | 1991-03-27 | Ici Canada Inc | Vesiculated polymer granules and paper made therefrom |
| CN1130634A (en) * | 1994-08-12 | 1996-09-11 | 罗姆和哈斯公司 | Encapsulated hydrophilic polymers and their preparation |
| US6139961A (en) * | 1998-05-18 | 2000-10-31 | Rohm And Haas Company | Hollow sphere organic pigment for paper or paper coatings |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960583A (en) * | 1974-05-02 | 1976-06-01 | Philadelphia Quartz Company | Method of preparing modified hollow, largely spherical particles by spray drying |
| US4427836A (en) * | 1980-06-12 | 1984-01-24 | Rohm And Haas Company | Sequential heteropolymer dispersion and a particulate material obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent |
| US4726986A (en) * | 1986-09-17 | 1988-02-23 | Westinghouse Electric Corp. | Decorative laminates having a thick chemical resistant outer layer |
| US4806207A (en) * | 1987-02-15 | 1989-02-21 | The Dow Chemical Company | Structured latex particles having reinforcing and opacity characteristics |
| CA1303437C (en) * | 1988-02-29 | 1992-06-16 | Nobuo Kawahashi | Hollow polymer particles, process for production thereof, and use thereof as pigment |
| JPH0791390B2 (en) * | 1989-06-23 | 1995-10-04 | 日本ゼオン株式会社 | Latex containing hollow polymer particles and method for producing the same |
| JP2872710B2 (en) * | 1989-10-27 | 1999-03-24 | 三井化学株式会社 | Synthetic resin emulsion and method for producing the same |
| US5622599A (en) * | 1994-06-28 | 1997-04-22 | Sproule; Barry | Method and apparatus for coating pulp products |
| US6020961A (en) * | 1995-11-30 | 2000-02-01 | Merlin Gesellschaft Fuer Mikrobiologische Diagnostik Mbh | Nephelometer |
| US6020435A (en) * | 1997-11-05 | 2000-02-01 | Rohm And Haas Company | Process for preparing polymer core shell type emulsions and polymers formed therefrom |
| US20020197469A1 (en) * | 1998-10-26 | 2002-12-26 | Richard Roy Clikeman | Particles and a process for preparing the same |
| AU2002317533A1 (en) * | 2002-01-07 | 2003-07-24 | Rohm And Haas Company | Process for preparing emulsion polymers and polymers formed therefrom |
| TWI227725B (en) * | 2002-03-12 | 2005-02-11 | Rohm & Haas | Heat resistant non-pigmented inks |
-
2005
- 2005-04-20 US US11/110,506 patent/US20050236125A1/en not_active Abandoned
- 2005-04-22 CN CNB2005100677003A patent/CN100417766C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594363A (en) * | 1985-01-11 | 1986-06-10 | Rohm And Haas Company | Production of core-sheath polymer particles containing voids, resulting product and use |
| EP0419206A1 (en) * | 1989-09-21 | 1991-03-27 | Ici Canada Inc | Vesiculated polymer granules and paper made therefrom |
| CN1130634A (en) * | 1994-08-12 | 1996-09-11 | 罗姆和哈斯公司 | Encapsulated hydrophilic polymers and their preparation |
| US6139961A (en) * | 1998-05-18 | 2000-10-31 | Rohm And Haas Company | Hollow sphere organic pigment for paper or paper coatings |
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| Publication number | Publication date |
|---|---|
| CN1690307A (en) | 2005-11-02 |
| US20050236125A1 (en) | 2005-10-27 |
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