CN101928534A - Single-component low temperature self-crossing emulsion adhesive for paper and plastic compounds and preparing method thereof - Google Patents
Single-component low temperature self-crossing emulsion adhesive for paper and plastic compounds and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a single-component low temperature self-crossing emulsion adhesive for paper and plastic compounds and a preparing method thereof. The raw materials of the self-crossing emulsion adhesive comprise the following components in part by weight: 100-150 parts of de-ionized water, 0.8-3.0 parts of emulsifier, 20-40 parts of nuclear layer monomer, 30-50 parts of interlayer monomer, 20-40 parts of shell layer monomer, and 0.2-0.6 part of initiator. The invention uses a small amount of anionic emulsifier to prepare nuclear emulsion, uses polymerisable emulsifier to prepare interlayer and shell layer pre-emulsion, and adopts semi-continuous seeded low emulsion polymerization process to prepare emulsion particles that have a three-layer core-shell microstructure to obtain the exquisite and stable emulsion. The product has no organic solvent, and does not release methanal, contains no APEO and no phthalate; the film coating has high transparency, high water resistance and high heat and humidity resistance; and the emulsion adhesive is applied to plastic and paper compounds, has high adhesive strength, peel strength and permanent adhesion, is also compatible to oil and ink and has high oil/ink transferring rate.
Description
Technical field
It is compound with polyacrylic ester tackiness agent emulsion to the present invention relates to paper, and it is compound with single-component low temperature self-crossing emulsion sizing agent and preparation method thereof particularly to relate to a kind of paper, and this sizing agent is applied to the compound sticking of plastics film and paper printed matter.
Background technology
Paper is compound to be to utilize tackiness agent that polyethylene, polypropylene (BOPP) or PET film and paper printed matter are combined with each other, make the level and smooth more light of printed matter surface, is rich in stereoscopic sensation, also play anti-moisture and soil-repellent, false proof, effect such as folding is wear-resisting simultaneously, be widely used in wrapping material, hard-cover books, decorative building material etc.The application request paper-plastic lamination adhesive all has good bonding force to the plastics film surface of polar paper surface and nonpolar low surface energy, and printing ink is had good affinity.
Polyacrylate(s) emulsion-type paper-plastic lamination adhesive has nontoxic pollution-free, synthesising coated easy, advantage such as mechanical property is adjustable, adhesive power is strong, but also have hot sticky cold crisp, the transparency, tack, bonding strength is relatively poor, ratio of printing ink transfer is not high, the bounding force moisture-proof thermal environment is relatively poor, and applied defect such as foaming, delamination.At these problems, carry out particle structure design and cross-linking modified research and have important practical significance.NMA be the cross-linking monomer that generally adopts at present (CN 101597355, CN101597355, CN1730547), but its crosslinking temperature is higher, cures Diazolidinyl Urea in the process at high temperature, is unfavorable for environmental protection and HUMAN HEALTH.Utilize GMA and the acrylic ester copolymer that contains the reactive hydrogen side group, can obtain epoxy self-cross linking type emulsion (USP 5225460).In recent years, and the normal temperature crosslinked technology of ketone hydrazine (DAAM/ADH) (USP 6262169, CN 101775189A, and CN101092470, CN101397350 CN1908022) receives much concern.The crosslinking technological that acetoacetyl (AAEM) and diamine reactant generate enamine also become the research focus (USP 5998543, WO2003051990, CN1438253, CN101348595).Introduced Michael reaction among the USP 5643977, mixed crosslinked with the polymer emulsion of band unsaturated carbon carbon double-bond lateral group by the ACRYLIC EMULSION of band methylene radical reactive hydrogen side group.Adopt emulsion polymerization technology to prepare the cinepazid polymer emulsion of band reactive chlorine side group and the cinepazid polymer emulsion of band pendant tertiary amine group respectively among the CN101538341, the two mixing is obtained room temperature self-crosslinking styrene-acrylic emulsion.With the monomer and the Acrylic Acid Monomer copolymerization of alkoxyl silicone, utilize the siloxanes hydrolytie polycondensation can form the Si-O-Si crosslinking structure (USP 5322890, CN1400243, CN101092468).Adopt among the CN 101597355 that to add aziridine crosslinked with the carboxyl reaction realization; With the linking agent that contains the NCO group can with the active hydrogen reaction in the acrylic ester emulsion, (CN 101580682, CN1517422) but the packaged form of two components is not easy to accumulating.
Summary of the invention
The objective of the invention is to propose a kind of preparation method, to improve the application performance of acrylate adhesive with multiple cross-linked interpenetrating(polymer)networks polyacrylate dispersion sizing agent of three-layer nuclear shell structure.
The present invention prepares middle layer and shell pre-emulsion with a small amount of anionic emulsifier preparation nuclear emulsion with the polymerizable emulsification system, adopts the low soap emulsion polymerization technique of semi-continuous seed, makes the stable emulsion of excellent performance; Design has the difference in functionality monomer, the three-layer nuclear shell structure that cross-linking monomer is formed, stratum nucleare mainly adopts the lipophilicity hard monomer, polar monomer and cross-linking monomer are introduced in the middle layer, utilize reactive behavior between the polar group and multiple pair of key of polyfunctional monomer, between stratum nucleare and shell, realize crosslinked " bridge formation " effect, improve cohesive strength and toughness, a large amount of polar monomer (the AA of outer employing, GMA, HA) carry out hydrogen bond and covalently cross-linked, be aided with acetoacetyl/diamines, metal ion crosslinked promotes system, promote that further emulsion particle merges crosslinked film forming, it is fine and smooth stable to make emulsion, the transparency of filming is good, cohesive strength, adhesive power obtains good balance, and has good water-fast moisture resistance properties.
The object of the invention is achieved through the following technical solutions:
The compound single-component low temperature self-crossing emulsion sizing agent of using of paper, in mass fraction, composition of raw materials comprises following component:
100～150 parts of deionized waters
0.8～3.0 part of emulsifying agent
20～40 parts mutually of nuclear layer monomer
30～50 parts mutually of middle layer monomers
20～40 parts mutually of shell monomers
0.2～0.6 part of initiator
0.025～0.3 part of chain-transfer agent
0.2～0.5 part of buffer reagent
0.05～0.15 part in oxygenant
0.05～0.15 part of reductive agent
0.5～5 part of neutralizing agent
0.2～2 part of linking agent
By weight percentage, described emulsifying agent by the stratum nucleare that accounts for (30～50) % with the middle layer of emulsifying agent, (30～50) % with emulsifying agent and 20～40) shell of % forms with emulsifying agent; Described stratum nucleare adopts conventional anionic emulsifier with emulsifying agent; Middle layer and shell adopt polymerisable emulsifier with emulsifying agent, are selected from 2-acrylamido-2-methyl-propyl sulfonic acid, allyl group hydroxypropyl azochlorosulfonate acid sodium, alkylamidoalkyl sodium vinyl sulfonate, sodium vinyl sulfonate, styryl sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic acid sodium salt and 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium salt one or both;
By weight percentage, described nuclear layer monomer is made up of 75～85% lipophilicity monomer, 1～3% hydrophilic monomer and 10～25% semi-hydrophilic monomers; Described lipophilicity monomer is one or both in vinylformic acid butyl, heptyl, nonyl, decyl, isooctyl acrylate, 4-methyl-2-vinylformic acid pentyl ester and the 2 ethyl hexyl acrylate; Described hydrophilic monomer is hydroxyethyl acrylate, vinylformic acid hydroxypropyl ester, methacrylic acid hydroxyethyl ester or hydroxypropyl methacrylate; Described semi-hydrophilic monomer is methyl acrylate, methyl methacrylate, ethyl propenoate and/or ethylacrylic acid methyl esters;
By weight percentage, described middle layer monomer comprises 85～97% acrylate monomer, 1～5% polar monomer and 0.4～1.5% cross-linking monomer mutually; Described acrylate monomer is multiple in methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate and the isooctyl acrylate ester; Described polar monomer is that vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, maleic anhydride, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, acrylamide, mass ratio are mixture, N-vinyl pyrrolidone, N-caprolactam and/or the N,N-DMAA of 1: 1 glycidyl methacrylate and acrylamide; Described cross-linking monomer is Vinylstyrene, diallyl maleate, ethylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediyl ester, 1,8-ethohexadiol diacrylate, Viscoat 295, trimethylammonium vinylformic acid pentaerythritol ester, tetraethylene glycol dimethacrylate or tri (propylene glycol) diacrylate;
By weight percentage, described shell monomers is made up of 90～95% acrylate monomer, 2～10% polar monomer and 0.05～2% crosslinking accelerator; Described acrylate monomer is multiple in methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, isooctyl acrylate ester and the lauryl methacrylate(LMA); Described polar monomer is that vinylformic acid, mass ratio are 1: 1 glycidyl methacrylate and acrylamide mixture, methacrylic acid and/or glycidyl methacrylate; Described crosslinking accelerator is vinyltriethoxysilane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane or glycidyl ether propoxy-methyldiethoxysilane;
Described initiator is ammonium persulphate, Potassium Persulphate or 2,2-azo diisobutyl amidine amine dihydrochloride; Described chain-transfer agent is a n-dodecyl mercaptan; Described buffer reagent is NaHCO
3
Described oxygenant is a tertbutyl peroxide; Described reductive agent is rongalite or sodium bisulfite;
Described neutralizing agent is ammoniacal liquor, quadrol, triethylamine or trolamine;
Described linking agent is 2,2,4-trimethylammonium hexanedioyl two [2-ethyl aziridine], 1,1-azelaoyl two [2-methylaziridine], 1, in 1-(1, the 3-phenylene dicarbonyl) two [2-methylaziridines], acetic acid zirconium ammonium, zinc acetate ammonium, chromium acetate and the zinc acetate one or both.
Be further to realize the object of the invention, described stratum nucleare is selected from sulfo-succinic acid Nonyl pheno (10) ether-ether disodium (MS21), ethoxylated alkyl ether ammonium sulfate (CO-436), oxyethyl group disodium sulfosuccinate, sodium alkyl naphthalene sulfonate, alkyl alcohol polyoxyethylene ammonium sulfate, alkyl ethoxylated ammonium sulfate, dioctyl sodium sulphosuccinate and the isopropyl naphthalene sodium sulfonate one or both with emulsifying agent.
By weight percentage, described middle layer monomer also comprises 0～5% vinyl monomer mutually; Described vinyl monomer is vinylbenzene, vinyl acetate, vinyl cyanide, vinylchlorid or tertiary ethylene carbonate.
Described composition of raw materials also comprises 0-10 part solubility promoter, and described fusing assistant is one or both in lauryl alcohol ester, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, glycol dimethyl ether and the diethylene glycol ether acetic ester.
Described composition of raw materials also comprises 0.05～1.0 part of 0.05～1.0 part of moistening flatting agent and defoamer; Described moistening flatting agent BYK 346 or BYK348 (being polyether-modified polydimethylsiloxane/dipropylene glycol monomethyl ether solution); Described defoamer is silicone antifoam agent BYK024 (chemical constitution is organic silicon modified by polyether/dipropylene glycol monomethyl ether solution) and/or BYK019 (chemical constitution is broken bubble polymkeric substance and polysiloxane mixture).
The compound preparation method with the single-component low temperature self-crossing emulsion sizing agent of above-mentioned paper comprises the steps:
(1) will fill a prescription in deionized water weight 20～40%, nuclear layer monomer phase, anionic emulsifier carry out pre-emulsification and obtain pre-emulsion A;
(2) get deionized water weight in the prescription 20～40%, middle layer monomer phase, polymerizable emulsifier carry out pre-emulsification and obtain pre-emulsion B;
(3) get deionized water weight in the prescription 20～40%, outer shell monomer phase, polymerizable emulsifier carry out pre-emulsification and obtain pre-emulsion C;
(4) initiator being mixed with weight percent concentration is 10～20% aqueous solution D; It is 10～20% aqueous solution E that reductive agent is mixed with weight percent concentration; It is 15～30% aqueous solution F that neutralizing agent is mixed with weight percent concentration;
(5) in container, add deionized water weight 5～15%, 5～15% preparations of buffer reagent sodium bicarbonate, initiator solution D weight obtain bed material, heat up 75～78 ℃, add 3～12% of pre-emulsion A weight, reaction formation seed emulsion; Controlled temperature is 78～82 ℃, drips 20～40% of residue pre-emulsion A and initiator solution D weight, and insulation 0.5～1h carries out slaking, drips 20～40% of pre-emulsion B and initiator solution D weight then, and insulation 0.5～1h carries out slaking; Drip 20～40% of pre-emulsion C and initiator solution D weight again; Dropwise the back and add chain-transfer agent; Be warming up to 84～90 ℃, insulation 0.5～1h; Be cooled to 63～70 ℃ then, be incubated 15～30min after adding oxygenant, be incubated 0.5～1h after dripping reductive agent aqueous solution E again, eliminate the residual free monomer; Be cooled to below 40 ℃, stir adding neutralizing agent aqueous solution F adjusting pH value 6～8 down, add linking agent, promptly obtain the acrylate adhesive emulsion.
With respect to prior art, the present invention has following effect:
The present invention prepares middle layer and shell pre-emulsion with a small amount of anionic emulsifier preparation nuclear emulsion with the polymerizable emulsification system, adopts pre-emulsification semi-continuous seed emulsion polymerization technology, hangs down the soap letex polymerization, makes few stable fine and smooth emulsion of slagging tap; Design by particle structure, introduce polyfunctional acrylic ester, carboxyl/epoxy group(ing)/amide group, the multiple interpenetrating(polymer)networks cross-linking system of vinylsiloxane, and acetoacetyl/diamines crosslinked (or carbonyl/hydrazine is crosslinked), the crosslinked promotion system of metal ion (or polyfunctional aziridine), make emulsion particle with three layers of microfacies structure of nucleocapsid; Do not contain organic solvent, release formaldehyde does not contain the violated chemical of APEO, phthalic ester and so on.Can realize low-temperature self-crosslinking, it is compound to be applied to paper, good with the printing ink affinity, adhesive power, stripping strength and hold the viscous force height, and water-fast wet-hot aging performance is good.
The compound following performance index that reach of paper of the present invention with low-temperature self-crosslinking sizing agent emulsion:
Solid content: 40～50%
PH value: 7.0～8.0
Viscosity: 200～300mPas
Surface tension: 35～38mN/m
Glued membrane glossiness: 65～70%
Package stability:＞6 months
Mechanical stability (the centrifugal 30min of 3000rpm): no breakdown of emulsion layering
Freeze-thaw stability: qualified
Initial bonding strength (steel ball number): 7
Hold viscous force＞20h
180 ° of stripping strength:＞5.0N/cm
Ratio of printing ink transfer: 100%
Impression, concavo-convex test: non-foaming
Embodiment
For better understanding the present invention, the present invention is described further below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1:
(unit is the compound gluing agent emulsion of table 1 paper E1 monomer prescription: g)
Annotate: HA refers to that mass ratio is 1: 1 the glycidyl methacrylate and the mixture of acrylamide
Synthetic method:
The preparation of nuclear emulsion: earlier 30g deionized water, 0.3g sulfo-succinic acid Nonyl pheno (10) ether-ether disodium (MS21), nuclear layer monomer phase I are carried out pre-emulsification and obtain pre-emulsion A; Getting 0.4g ammonium persulphate (APS), to be mixed with weight percent concentration be 3% initiator solution D (APS aqueous solution D); Getting the 0.15g rongalite, to be mixed with weight percent concentration be 10～20% aqueous solution E.10% preparation that adds 15g deionized water, 0.3g buffer reagent sodium bicarbonate, APS aqueous solution D weight in four-hole boiling flask obtains bed material, heats up 78 ℃, and 3% reaction that adds the pre-emulsion A gross weight of 3% weight forms seed emulsion; Heat up 80 ℃, begin to drip residue pre-emulsion A, and drip 30% of APS aqueous solution D gross weight synchronously, insulation 0.5h makes the nuclear emulsion;
The preparation of middle layer and outer pre-emulsion: get 35g deionized water, 2-acrylamido-2-methyl-propyl sulfonic acid 0.4g, middle layer monomer mutually II carry out pre-emulsification and obtain pre-emulsion B; Getting 30g deionized water, 0.4g sodium vinyl sulfonate, shell monomers phase III carries out pre-emulsification and obtains pre-emulsion C;
Middle layer and shell batch feed: in the nuclear emulsion, drip pre-emulsion B, and drip 30% of APS aqueous solution D gross weight synchronously; Insulation 0.5h carries out slaking, begins to drip pre-emulsion C, and drips residue APS aqueous solution D synchronously; After dropwising, add the positive Dodecyl Mercaptan of 0.025g;
Be warming up to 90 ℃ after dropwising then, insulation 1h; Lower the temperature 65 ℃, add 0.15g tertbutyl peroxide TBHP, insulation 15～30min drips rongalite aqueous solution E again, eliminates the residual free monomer;
Be cooled to below 40 ℃, with weight percent concentration be 20% ethylenediamine solution to regulate ph value of emulsion be 7, add to get 1.5g acetic acid zirconium ammonium to be mixed with weight percent concentration be 20% the aqueous solution, add in the emulsion, 200 mesh filter screens filter discharging, promptly obtain acrylate adhesive emulsion E1.
Embodiment 2:
(unit is the compound gluing agent emulsion of table 2 paper E2 monomer prescription: g)
Synthetic method:
The preparation of nuclear emulsion: earlier 32g deionized water, 0.25g ethoxylated alkyl ether ammonium sulfate (CO-436), nuclear layer monomer phase I are carried out pre-emulsification and obtain pre-emulsion A; Get 2,2-azo diisobutyl amidine amine dihydrochloride (V50) 0.4g preparation weight percent concentration is 3% initiator solution D; Getting the 0.15g sodium bisulfite, to be mixed with weight percent concentration be 10～20% aqueous solution E.10% preparation that adds 12g deionized water, 0.3g buffer reagent sodium bicarbonate, APS aqueous solution D gross weight in four-hole boiling flask obtains bed material, heats up 75 ℃, and 8% reaction that adds pre-emulsion A gross weight forms seed emulsion; Heat up 78 ℃, begin to drip residue pre-emulsion A, and drip 30% of V50 aqueous solution D gross weight synchronously, insulation 0.5h makes the nuclear emulsion;
The preparation of middle layer and outer pre-emulsion: get 36g deionized water, 0.4g alkylamidoalkyl sodium vinyl sulfonate, middle layer monomer mutually II carry out pre-emulsification and obtain pre-emulsion B; Getting 30g deionized water, 0.4g methacryloxy ethyl sulfonic acid sodium, shell monomers phase III carries out pre-emulsification and obtains pre-emulsion C;
Middle layer and shell batch feed: in the nuclear emulsion, drip pre-emulsion B, and drip 30% of V50 aqueous solution D gross weight synchronously; Insulation 0.5h carries out slaking, begins to drip pre-emulsion C, and drips remaining V50 aqueous solution D synchronously; After dropwising, add the positive Dodecyl Mercaptan of 0.05g;
Be warming up to 84 ℃ after dropwising, insulation 1h;
Lower the temperature 65 ℃, add 0.15g tertbutyl peroxide TBHP, insulation 15～30min drips aqueous solution of sodium bisulfite E again, eliminates the residual free monomer;
Be cooled to below 40 ℃, regulate ph value of emulsion 7.5 with the trolamine aqueous solution that with weight percent concentration is 20%, getting the 0.8g adipic dihydrazide, to be mixed with weight percent concentration be 20% the aqueous solution, add in the emulsion, 200 mesh filter screens filter discharging, promptly obtain acrylate adhesive emulsion E2.
Embodiment 3:
(unit is the compound gluing agent emulsion of table 3 paper E3 monomer prescription: g)
Synthetic method:
The preparation of nuclear emulsion: earlier 32g deionized water, 0.3g oxyethyl group disodium sulfosuccinate, nuclear layer monomer phase I are carried out pre-emulsification and obtain pre-emulsion A; Getting 0.4g ammonium persulphate (APS) preparation weight percent concentration is 3% initiator solution D; Getting the 0.15g rongalite, to be mixed with weight percent concentration be 10～20% aqueous solution E.10% preparation that adds 18g deionized water, 0.3g buffer reagent sodium bicarbonate, APS aqueous solution D gross weight in four-hole boiling flask obtains bed material, heats up 80 ℃, and 8% reaction that adds pre-emulsion A gross weight forms seed emulsion; Heat up 82 ℃, begin to drip residue pre-emulsion A, and drip 30% of APS aqueous solution D gross weight synchronously, insulation 0.5h makes the nuclear emulsion;
The preparation of middle layer and outer pre-emulsion: get 30g deionized water, 0.4g styryl sodium sulfonate, middle layer monomer mutually II carry out pre-emulsification and obtain pre-emulsion B; Getting 30g deionized water, 0.4g allyl group hydroxypropyl azochlorosulfonate acid sodium, shell monomers phase III carries out pre-emulsification and obtains pre-emulsion C;
Middle layer and shell batch feed: in the nuclear emulsion, drip pre-emulsion B, and drip 30% of APS aqueous solution D gross weight synchronously; Insulation 0.5h carries out slaking, begins to drip pre-emulsion C, and drips residue APS aqueous solution D synchronously; After dropwising, add the positive Dodecyl Mercaptan of 0.035g;
Be warming up to 88 ℃ after dropwising, insulation 1h;
Lower the temperature 65 ℃, add 0.15g tertbutyl peroxide TBHP, insulation 15～30min drips rongalite aqueous solution E again, eliminates the residual free monomer;
Be cooled to below 40 ℃, with weight percent concentration is that 20% triethylamine aqueous solution is regulated pH value 7.8, get 1.5g 2,2, it is 20% the aqueous solution that 4-trimethylammonium hexanedioyl two [2-ethyl aziridine] is mixed with weight percent concentration, add in the emulsion, 200 mesh filter screens filter discharging, promptly obtain acrylate adhesive emulsion E3.
Embodiment 4:
(unit is the compound gluing agent emulsion of table 4 paper E4 monomer prescription: g)
Synthetic method:
The preparation of nuclear emulsion: earlier 24g deionized water, 0.3g dioctyl sodium sulphosuccinate, nuclear layer monomer phase I are carried out pre-emulsification and obtain pre-emulsion A; Getting 0.4g ammonium persulphate (APS) preparation weight percent concentration is 3% initiator solution D; Getting the 0.15g sodium bisulfite, to be mixed with weight percent concentration be 10～20% aqueous solution E.10% preparation that adds 20g deionized water, 0.3g buffer reagent sodium bicarbonate, APS aqueous solution D gross weight in four-hole boiling flask obtains bed material, heats up 78 ℃, and 8% reaction that adds pre-emulsion A gross weight forms seed emulsion; Heat up 82 ℃, begin to drip residue pre-emulsion A, and drip 30% of APS aqueous solution D gross weight synchronously, insulation 0.5h makes the nuclear emulsion;
The preparation of middle layer and outer pre-emulsion: get 36g deionized water, 2-acrylamide-2-methyl propane sulfonic acid sodium salt 0.4g, middle layer monomer mutually II carry out pre-emulsification and obtain pre-emulsion B; Get 30g deionized water, 0.4g allyloxy nonyl phenolic ether and sulfonated bodies thereof, shell monomers phase III is carried out pre-emulsification and is obtained pre-emulsion C;
Middle layer and shell batch feed: in the nuclear emulsion, drip pre-emulsion B, and drip 30% of APS aqueous solution D gross weight synchronously; Insulation 0.5h carries out slaking, begins to drip pre-emulsion C, and drips residual A PS aqueous solution D synchronously; After dropwising, add the positive Dodecyl Mercaptan of 0.10g;
Be warming up to 90 ℃ after dropwising, insulation 1h;
Lower the temperature 65 ℃, add 0.15g tertbutyl peroxide TBHP, insulation 15～30min drips aqueous solution of sodium bisulfite E again, eliminates the residual free monomer;
Be cooled to below 40 ℃, with weight percent concentration is that to regulate ph value of emulsion be 7.5 for 20% ethylenediamine solution, get 1.2g 1,1-(1, the 3-phenylene dicarbonyl) to be mixed with weight percent concentration be 20% the aqueous solution to two [2-methylaziridines], add in the emulsion, 200 mesh filter screens filter discharging, promptly obtain acrylate adhesive emulsion E4.
Embodiment 5:
(unit is the compound gluing agent emulsion of table 5 paper E5 monomer prescription: g)
Synthetic method:
The preparation of nuclear emulsion: earlier 35g deionized water, 0.3g isopropyl naphthalene sodium sulfonate, nuclear layer monomer phase I are carried out pre-emulsification and obtain pre-emulsion A; Getting 0.4g ammonium persulphate (APS) preparation weight percent concentration is 3% initiator solution D; Getting the 0.15g rongalite, to be mixed with weight percent concentration be 10～20% aqueous solution E.10% preparation that adds 20g deionized water, 0.3g buffer reagent sodium bicarbonate, APS aqueous solution D gross weight in four-hole boiling flask obtains bed material, heats up 78 ℃, and 8% reaction that adds pre-emulsion A gross weight forms seed emulsion; Heat up 84 ℃, begin to drip residue pre-emulsion A, and drip 30% of APS aqueous solution D gross weight synchronously, insulation 0.5h makes the nuclear emulsion;
The preparation of middle layer and outer pre-emulsion: get 35g deionized water, 0.4g sodium vinyl sulfonate, middle layer monomer mutually II carry out pre-emulsification and obtain pre-emulsion B; Getting 30g deionized water, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium salt 0.4g, shell monomers phase III carries out pre-emulsification and obtains pre-emulsion C;
Middle layer and shell batch feed: in the nuclear emulsion, drip pre-emulsion B, and drip 30% of APS aqueous solution D gross weight synchronously; Insulation 0.5h carries out slaking, begins to drip pre-emulsion C, and drips residual A PS aqueous solution D synchronously; After dropwising, add the positive Dodecyl Mercaptan of 0.045g;
Be warming up to 90 ℃ after dropwising, insulation 1h;
Lower the temperature 65 ℃, add 0.15g tertbutyl peroxide TBHP, insulation 15～30min drips rongalite aqueous solution E again, eliminates the residual free monomer;
Be cooled to below 40 ℃, with weight percent concentration is that to regulate ph value of emulsion be 7.5 for 20% the trolamine aqueous solution, getting the 0.85g adipic dihydrazide, to be mixed with weight percent concentration be 20% the aqueous solution, add in the emulsion, 200 mesh filter screens filter discharging, promptly obtain acrylate adhesive emulsion E5.
Embodiment 6:
(unit is the compound gluing agent emulsion of table 6 paper E6 monomer prescription: g)
Synthetic method:
The preparation of nuclear emulsion: earlier 30g deionized water, 0.3g isopropyl naphthalene sodium sulfonate, nuclear layer monomer phase I are carried out pre-emulsification and obtain pre-emulsion A; Getting 0.4g ammonium persulphate (APS) preparation weight percent concentration is 3% initiator solution D; Getting the 0.15g sodium bisulfite, to be mixed with weight percent concentration be 10～20% aqueous solution E.10% preparation that adds 20g deionized water, 0.3g buffer reagent sodium bicarbonate, APS aqueous solution D weight in four-hole boiling flask obtains bed material, heats up 78 ℃, and 8% reaction that adds pre-emulsion A weight forms seed emulsion; Heat up 80 ℃, begin to drip residue pre-emulsion A, and drip 30% of APS aqueous solution D weight synchronously, insulation 0.5h makes the nuclear emulsion;
The preparation of middle layer and outer pre-emulsion: get 40g deionized water, 0.4g sodium vinyl sulfonate, middle layer monomer mutually II carry out pre-emulsification and obtain pre-emulsion B; Getting 30g deionized water, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium salt 0.4g, shell monomers phase III carries out pre-emulsification and obtains pre-emulsion C;
Middle layer and shell batch feed: in the nuclear emulsion, drip pre-emulsion B, and drip 30% of APS aqueous solution D gross weight synchronously; Insulation 0.5h carries out slaking, begins to drip pre-emulsion C, and drips residual A PS aqueous solution D synchronously; After dropwising, add the positive Dodecyl Mercaptan of 0.075g;
Be warming up to 85 ℃ after dropwising, insulation 1h;
Lower the temperature 65 ℃, add 0.15g tertbutyl peroxide TBHP, insulation 15～30min drips aqueous solution of sodium bisulfite E again, eliminates the residual free monomer;
Be cooled to below 40 ℃, with weight percent concentration be 20% ethylenediamine solution to regulate ph value of emulsion be 7.5, getting the 0.9g zinc acetate, to be mixed with weight percent concentration be 20% the aqueous solution, adds in the emulsion, promptly obtains acrylate adhesive emulsion E6.
The compound gluing agent emulsion of the paper that the foregoing description 1～6 is obtained carries out multiple film test on bridge-type dry type composite film machine respectively, and setting drying tunnel temperature is 60 ℃, 40 ℃ of press bonding roller temperature, pressure is 15kgf, and with the compound 320g enamelled paper of PET film (thickness 20 μ m), the butt spread is about 3.0g/m
2, adopt electronic tensile machine to measure 180 ° of stripping strengths (with reference to GB/T2792-1998); Composite membrane was placed 30 days in climatic chamber (50 ℃, humidity 80%), measured stripping strength once more, the persistence of cohesive strength (characterizing) under the checking hot and humid environment with the stripping strength conservation rate; Measure water tolerance (characterizing with water-intake rate) with reference to GB-15330-1994, the result is as shown in table 7:
The application performance of the compound gluing agent emulsion of table 7 paper
This shows, the prepared acrylic ester emulsion sizing agent of the present invention shows that stripping strength height, wet-hot aging performance are good, the excellent properties of water-tolerant, in conjunction with the fundamental property index of aforementioned sizing agent emulsion, the paper that the present invention makes is compound can to satisfy application requiring with low-temperature self-crosslinking sizing agent emulsion.
Can be equipped with auxiliary agent concrete with reference to following application example before using applying glue, earlier acrylic ester emulsion and staybelite emulsion pieced together being mixed evenly, the adding solubility promoter adds moistening flatting agent, defoamer, sanitas more successively and is uniformly dispersed, to improve sizing efficiency;
Application example prescription (meter by weight):
Acrylic ester emulsion 1000
Staybelite emulsion 0～100
Solubility promoter (diethylene glycol ether acetic ester) 0～10
Moistening flatting agent BYK 346 or BYK348 0.5～10
Defoamer (BYK024BYK019) 0.5～10
Sanitas (Deuchem MB-11) 0.5～5
Acrylic ester emulsion is embodiment 1-6 preparation.Described solubility promoter can be one or both in lauryl alcohol ester, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, glycol dimethyl ether and the diethylene glycol ether acetic ester.Deuchem MB-11 is produced by the modest company of Shanghai moral, and moistening flatting agent BYK 346 and/or BYK348, defoamer BYK024BYK019 are provided by German Bi Ke chemistry (Guangzhou).
Above-mentioned embodiment has just been enumerated exemplary embodiments of the present invention; can only think explanation of the present invention rather than restriction the present invention; those skilled in the art can do respective change and improvement under the specification sheets indication, but should think in patent book protection domain of the present invention.
Claims (6)
1. the compound single-component low temperature self-crossing emulsion sizing agent of using of paper, it is characterized in that: in mass fraction, its composition of raw materials comprises following component:
100～150 parts of deionized waters
0.8～3.0 part of emulsifying agent
20～40 parts mutually of nuclear layer monomer
30～50 parts mutually of middle layer monomers
20～40 parts mutually of shell monomers
0.2～0.6 part of initiator
0.025～0.3 part of chain-transfer agent
0.2～0.5 part of buffer reagent
0.05～0.15 part in oxygenant
0.05～0.15 part of reductive agent
0.5～5 part of neutralizing agent
0.2～2 part of linking agent
By weight percentage, described emulsifying agent by the stratum nucleare that accounts for (30～50) % with the middle layer of emulsifying agent, (30～50) % with emulsifying agent and 20～40) shell of % forms with emulsifying agent; Described stratum nucleare adopts conventional anionic emulsifier with emulsifying agent; Middle layer and shell adopt polymerisable emulsifier with emulsifying agent, are selected from 2-acrylamido-2-methyl-propyl sulfonic acid, allyl group hydroxypropyl azochlorosulfonate acid sodium, alkylamidoalkyl sodium vinyl sulfonate, sodium vinyl sulfonate, styryl sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic acid sodium salt and 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium salt one or both;
By weight percentage, described nuclear layer monomer is made up of 75～85% lipophilicity monomer, 1～3% hydrophilic monomer and 10～25% semi-hydrophilic monomers; Described lipophilicity monomer is one or both in vinylformic acid butyl, heptyl, nonyl, decyl, isooctyl acrylate, 4-methyl-2-vinylformic acid pentyl ester and the 2 ethyl hexyl acrylate; Described hydrophilic monomer is hydroxyethyl acrylate, vinylformic acid hydroxypropyl ester, methacrylic acid hydroxyethyl ester or hydroxypropyl methacrylate; Described semi-hydrophilic monomer is methyl acrylate, methyl methacrylate, ethyl propenoate and/or ethylacrylic acid methyl esters;
By weight percentage, described middle layer monomer comprises 85～97% acrylate monomer, 1～5% polar monomer and 0.4～1.5% cross-linking monomer mutually; Described acrylate monomer is multiple in methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate and the isooctyl acrylate ester; Described polar monomer is that vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, maleic anhydride, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, acrylamide, mass ratio are mixture, N-vinyl pyrrolidone, N-caprolactam and/or the N,N-DMAA of 1: 1 glycidyl methacrylate and acrylamide; Described cross-linking monomer is Vinylstyrene, diallyl maleate, ethylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediyl ester, 1,8-ethohexadiol diacrylate, Viscoat 295, trimethylammonium vinylformic acid pentaerythritol ester, tetraethylene glycol dimethacrylate or tri (propylene glycol) diacrylate;
By weight percentage, described shell monomers is made up of 90～95% acrylate monomer, 2～10% polar monomer and 0.05～2% crosslinking accelerator; Described acrylate monomer is multiple in methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, isooctyl acrylate ester and the lauryl methacrylate(LMA); Described polar monomer is that vinylformic acid, mass ratio are 1: 1 glycidyl methacrylate and acrylamide mixture, methacrylic acid and/or glycidyl methacrylate; Described crosslinking accelerator is vinyltriethoxysilane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane or glycidyl ether propoxy-methyldiethoxysilane;
Described initiator is ammonium persulphate, Potassium Persulphate or 2,2-azo diisobutyl amidine amine dihydrochloride; Described chain-transfer agent is a n-dodecyl mercaptan; Described buffer reagent is NaHCO
3
Described oxygenant is a tertbutyl peroxide; Described reductive agent is rongalite or sodium bisulfite;
Described neutralizing agent is ammoniacal liquor, quadrol, triethylamine or trolamine;
Described linking agent is 2,2,4-trimethylammonium hexanedioyl two [2-ethyl aziridine], 1,1-azelaoyl two [2-methylaziridine], 1, in 1-(1, the 3-phenylene dicarbonyl) two [2-methylaziridines], acetic acid zirconium ammonium, zinc acetate ammonium, chromium acetate and the zinc acetate one or both.
2. the compound single-component low temperature self-crossing emulsion sizing agent of using of paper according to claim 1 is characterized in that: described stratum nucleare is selected from sulfo-succinic acid Nonyl pheno (10) ether-ether disodium (MS21), ethoxylated alkyl ether ammonium sulfate (CO436), oxyethyl group disodium sulfosuccinate, sodium alkyl naphthalene sulfonate, alkyl alcohol polyoxyethylene ammonium sulfate, alkyl ethoxylated ammonium sulfate, dioctyl sodium sulphosuccinate and the isopropyl naphthalene sodium sulfonate one or both with emulsifying agent.
3. the compound single-component low temperature self-crossing emulsion sizing agent of using of paper according to claim 1, it is characterized in that: described middle layer monomer also comprises 0～5% vinyl monomer mutually; Described vinyl monomer is vinylbenzene, vinyl acetate, vinyl cyanide, vinylchlorid or tertiary ethylene carbonate.
4. the compound single-component low temperature self-crossing emulsion sizing agent of using of paper according to claim 1, it is characterized in that: described composition of raw materials also comprises 0-10 part solubility promoter, and described fusing assistant is one or both in lauryl alcohol ester, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, glycol dimethyl ether and the diethylene glycol ether acetic ester.
5. the compound single-component low temperature self-crossing emulsion sizing agent of using of paper according to claim 1 is characterized in that: described functional agent comprises 0.05～1.0 part of 0.05～1.0 part of moistening flatting agent and defoamer; Described moistening flatting agent BYK 346 or BYK348; Described defoamer is silicone antifoam agent BYK024 and/or BYK019.
6. the compound preparation method with the single-component low temperature self-crossing emulsion sizing agent of the described paper of claim 1 is characterized in that comprising the steps:
(1) will fill a prescription in deionized water weight 20～40%, nuclear layer monomer phase, anionic emulsifier carry out pre-emulsification and obtain pre-emulsion A;
(2) get deionized water weight in the prescription 20～40%, middle layer monomer phase, polymerizable emulsifier carry out pre-emulsification and obtain pre-emulsion B;
(3) get deionized water weight in the prescription 20～40%, outer shell monomer phase, polymerizable emulsifier carry out pre-emulsification and obtain pre-emulsion C;
(4) initiator being mixed with weight percent concentration is 10～20% aqueous solution D; It is 10～20% aqueous solution E that reductive agent is mixed with weight percent concentration; It is 15～30% aqueous solution F that neutralizing agent is mixed with weight percent concentration;
(5) in container, add deionized water weight 5～15%, 5～15% preparations of buffer reagent sodium bicarbonate, initiator solution D weight obtain bed material, heat up 75～78 ℃, add 3～12% of pre-emulsion A weight, reaction formation seed emulsion; Controlled temperature is 78～82 ℃, drips 20～40% of residue pre-emulsion A and initiator solution D weight, and insulation 0.5～1h carries out slaking, drips 20～40% of pre-emulsion B and initiator solution D weight then, and insulation 0.5～1h carries out slaking; Drip 20～40% of pre-emulsion C and initiator solution D weight again; Dropwise the back and add chain-transfer agent; Be warming up to 84～90 ℃, insulation 0.5～1h; Be cooled to 63～70 ℃ then, be incubated 15～30min after adding oxygenant, be incubated 0.5～1h after dripping reductive agent aqueous solution E again, eliminate the residual free monomer; Be cooled to below 40 ℃, stir adding neutralizing agent aqueous solution F adjusting pH value 6～8 down, add linking agent, promptly obtain the acrylate adhesive emulsion.
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