CN100340717C - Nano emulsion type surface gluing agent - Google Patents
Nano emulsion type surface gluing agent Download PDFInfo
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- CN100340717C CN100340717C CNB2004100663237A CN200410066323A CN100340717C CN 100340717 C CN100340717 C CN 100340717C CN B2004100663237 A CNB2004100663237 A CN B2004100663237A CN 200410066323 A CN200410066323 A CN 200410066323A CN 100340717 C CN100340717 C CN 100340717C
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- acrylate
- type surface
- emulsion type
- methacrylate
- additive
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- 239000007908 nanoemulsion Substances 0.000 title claims description 27
- 238000004026 adhesive bonding Methods 0.000 title claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- -1 allyl sulfonate Chemical compound 0.000 claims abstract description 18
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 14
- DZMOLBFHXFZZBF-UHFFFAOYSA-N prop-2-enyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC=C DZMOLBFHXFZZBF-UHFFFAOYSA-N 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 229920000289 Polyquaternium Polymers 0.000 claims description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 244000085692 Cordia alliodora Species 0.000 claims description 9
- 235000004258 Cordia alliodora Nutrition 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 claims description 6
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 6
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 6
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 14
- 238000004513 sizing Methods 0.000 abstract description 14
- 239000003292 glue Substances 0.000 abstract description 12
- 229920002472 Starch Polymers 0.000 abstract description 9
- 239000008107 starch Substances 0.000 abstract description 9
- 235000019698 starch Nutrition 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 7
- 238000006386 neutralization reaction Methods 0.000 abstract description 5
- 239000011436 cob Substances 0.000 abstract description 4
- 238000005187 foaming Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920001800 Shellac Polymers 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 3
- 239000004208 shellac Substances 0.000 description 3
- 229940113147 shellac Drugs 0.000 description 3
- 235000013874 shellac Nutrition 0.000 description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- ICDUXFJWENHMAG-UHFFFAOYSA-N CC(O)C[Na] Chemical compound CC(O)C[Na] ICDUXFJWENHMAG-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- DGTOAFBVEDTEBA-UHFFFAOYSA-N sodium;prop-1-ene Chemical compound [Na+].[CH2-]C=C DGTOAFBVEDTEBA-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Abstract
The present invention relates to a nanometer emulsion type surface glue sizing agent. The present invention is characterized in that the nanometer emulsion type surface additive agent is prepared by mixing the components of the proportion by weight: 5 to 20% of polycarboxylate as dispersing agents, 0.5 to 50% allyl sulfonate or allyl phosphate, 0.1 to 10% of C5 to C8 alcohol, 15 to 60% of additive agent and 20 to 40% of deionized water, and adding 0.5 to 1.5% of sodium hydroxide for neutralization. When the surface glue sizing agent is used, the particle diameter of dispersing bodies is from 30 to 80 nm. The surface glue sizing agent and starch which are used for sizing the surface of paper together can largely enhance the strength of paper, obviously improve Cobb value, and effectively improve the smoothness, the stiffness and the printing adaptability of paper. The surface glue sizing agent and the starch have ultra-low foaming performance and favorable compatibility with other chemical products.
Description
Technical field:
The present invention relates to the technical field of Cypres, specifically a kind of nano emulsion type surface gluing agent.
Background technology:
In the file that retrieves at present, publication number CN1323318A has described a kind of method for preparing cationic styrene-acrylic acid ester emulsion in the presence of stabilizing agent.This method uses the oxidation waxy corn starch to be dispersant, will comprise that the mix monomer of styrene, methyl acrylate, ethyl acrylate and butyl acrylate carries out polymerization, obtains a kind of cation emulsion Cypres.This method is owing to use hydrophilic monomer and dispersant too much, thereby the paper surface hygroscopicity value is difficult to well be improved.
CN1402805A has described a kind of method for preparing the cinnamic acrylic ester emulsion surface sizing agent in the presence of the shellac slaine.This method is carried out polymerization with hydrophilic monomer and hydrophobic monomer or in the presence of emulsifying agent above-mentioned monomer is carried out emulsion polymerisation and mix the shellac metal salt solution again in the presence of the shellac slaine, benzene mixed ethene-(methyl) acrylic type dispersant solution promptly more at last.The Cypres particle diameter that this method makes about 100nm, is difficult to guarantee to be greatly improved simultaneously by the double-edged surface strength of sized paper usually.
CN1446233A has then described a kind of method of carrying out the emulsion polymerization prepared emulsion surface sizing agent in the aqueous solution of starch or starch derivatives.The Cypres particle diameter that this method makes also about 100nm, also is difficult to guarantee to be greatly improved simultaneously by the double-edged surface strength of sized paper usually.
Summary of the invention:
The object of the present invention is to provide a kind of improved nano emulsion type surface gluing agent, it can overcome in the prior art some shortcomings of paper strength, smoothness and deflection after the applying glue.
To achieve these goals, technical scheme of the present invention is: a kind of nano emulsion type surface gluing agent is characterized in that: described nano emulsion type surface additive is to be the C of the allylsulfonate of polycarboxylate salt dispersant, 0.5-50% of 5-20% or allyl phosphate, 0.1-10% by percentage by weight
5---C
8The additive of alcohol, 15-60% and after the deionized water of 20-40% mixes, the NaOH that adds 0.5-1.5% at last neutralizes.
A kind of nano emulsion type surface gluing agent is characterized in that: described nano emulsion type surface additive is to be that alcohol, the additive of 15-60% and the deionized water of 20-40% of C5---C8 of allyl quaternary ammonium salt, the 0.1-10% of polyquaternium dispersant, the 0.5-50% of 5-20% mixes by percentage by weight.
A kind of preparation method of nano emulsion type surface gluing agent is characterized in that: the preparation method of described nano emulsion type surface gluing agent is as follows: a, be the deionized water of 20-40%, the polycarboxylate salt dispersant of 5-20%, the allylsulfonate of 0.5-50% or the C of allyl phosphate and 0.1-10% with percentage by weight
5---C
8Alcohol mix the back and under nitrogen environment, be warming up to 80-90 ℃; The additive of b, adding 15-60% is incubated 15-30 minute down at 70-85 ℃, is cooled to room temperature; C, the NaOH that adds 0.5-1.5% at last neutralize, and filter discharging.
A kind of preparation method of nano emulsion type surface gluing agent is characterized in that: the preparation method of described nano emulsion type surface gluing agent is as follows: a, be the deionized water of 20-40%, the polyquaternium dispersant of 5-20%, the allyl quaternary ammonium salt of 0.5-50% and the C of 0.1-10% with percentage by weight
5---C
8Alcohol mix the back and under nitrogen environment, be warming up to 80-90 ℃; The additive of b, adding 15-60% is incubated 15-30 minute down at 70-85 ℃, is cooled to room temperature, filters discharging.
A kind of nano emulsion type surface gluing agent of the present invention during use is translucent polymer emulsion, and its dispersion particle diameters is between the 30-80 nanometer.This Cypres carries out top sizing with starch to paper, can increase substantially strength of paper, significantly improve the Cobb value, effectively improves the printing adaptability of smoothness, deflection and paper; And have ultralow foaming characteristic, with the good compatibility of other chemicals.
The specific embodiment:
The invention will be further described below in conjunction with drawings and Examples.
Difference with the prior art of the present invention is: described nano emulsion type surface additive is to be the C of the allylsulfonate of polycarboxylate salt dispersant, 0.5-50% of 5-20% or allyl phosphate, 0.1-10% by percentage by weight
5---C
8The additive of alcohol, 15-60% and after the deionized water of 20-40% mixes, the NaOH that adds 0.5-1.5% at last neutralizes; Described polycarboxylate salt dispersant is after being mixed by 10-40 part deionized water, 1-20 part isopropyl alcohol, 5-25 part maleic anhydride and 1-15 part acrylic acid, to heat in nitrogen environment to 60-100 ℃, and the sodium peroxydisulfate solution that adds 2-10 part 20% at last makes; Additive can be that the water of one or more and 10-20% of following material mixes: the alkylphenol ether sodium sulfate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, EHMA, styrene, divinylbenzene; Polycarboxylate salt dispersant's weight average molecular weight is 500-3500.
Described nano emulsion type surface additive is to be the polyquaternium dispersant of 5-20%, the allyl quaternary ammonium salt of 0.5-50%, the C of 0.1-10% by percentage by weight
5---C
8Alcohol, the additive of 15-60% and the deionized water of 20-40% mix; Polyquaternium dispersant wherein, be by 10-40 part deionized water, 1-20 part isopropyl alcohol, 10-40 part methylacryoyloxyethyl trimethyl ammonium chloride (DMC), 5-20 part acrylamide, be heated to 60-100 ℃ in nitrogen environment, the copperas solution and 1-10 part 20% hydrogen peroxide solution that add 2-10 part 1% again make; Additive can be that the water of one or more and 10-20% of following material mixes: azo two NSC 18620s, DTAB, softex kw, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, acrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, EHMA, styrene, divinylbenzene; The weight average molecular weight of polyquaternium dispersant is 800-4000.
The preparation method of described nano emulsion type surface gluing agent is as follows: a, be the deionized water of 20-40%, the polycarboxylate salt dispersant of 5-20%, the allylsulfonate of 0.5-50% or the C of allyl phosphate and 0.1-10% with percentage by weight
5---C
8Alcohol mix the back and under nitrogen environment, be warming up to 80-90 ℃; The additive of b, adding 15-60% is incubated 15-30 minute down at 70-85 ℃, is cooled to room temperature; C, the NaOH that adds 0.5-1.5% at last neutralize, and filter discharging.
The preparation method of described nano emulsion type surface gluing agent also can be as follows: a, be the deionized water of 20-40%, the polyquaternium dispersant of 5-20%, the allyl quaternary ammonium salt of 0.5-50% and the C of 0.1-10% with percentage by weight
5---C
8Alcohol mix the back and under nitrogen environment, be warming up to 80-90 ℃; The additive of b, adding 15-60% is incubated 15-30 minute down at 70-85 ℃, is cooled to room temperature, filters discharging.
Embodiment 1
In one 1000 milliliters four neck round-bottomed flasks, (all components amounts to 100 parts to add 13.8 parts, 1 part is equivalent to 7.24 grams, deionized water, 2.9 parts of isopropyl alcohols down together), and under nitrogen atmosphere, be warming up to 82 ℃, drip 4.83 part 20% sodium peroxydisulfate solution then simultaneously and by solution mixture that following component constituted: 22.8 parts of water, 11.6 parts of maleic anhydrides, 7.73 parts of acrylic acid.The reinforced time is 4 hours, the reinforced insulation 1 hour that finishes.Under 95 ℃, steam whole isopropyl alcohols then.Be cooled to room temperature, the sampling and measuring molecular weight.With 39.23 part of 35% NaOH neutralization, filter discharging.Obtain the polycarboxylate salt dispersant of 29.88% solid content, it is 1520 that gel chromatography (GPC) records weight average molecular weight.
In one 1000 milliliters four neck round-bottomed flasks, (all components amounts to 100 parts to add 33.48 parts, 1 part is equivalent to 7.85 grams, deionized water down together), add polycarboxylate salt dispersant's solution, 0.69 part of 2-hydroxypropyl sodium allylsulfonate and 0.69 part of isoamyl alcohol of 12.38 parts of above-mentioned preparations, and under nitrogen atmosphere, be warming up to 85 ℃.Drip 7.13 part 2.2% ammonium persulfate solution then simultaneously and by emulsion-type additive that following component constituted: 19.48 parts of water, 0.18 part dodecyl phenol ether sodium sulfate, 8.40 parts of butyl acrylates, 4.77 parts of methyl methacrylates, 11.52 part styrene, 0.76 part of acrylic acid.The reinforced time is 3 hours; After reinforced being all over, 85 ℃ are incubated 30 minutes down.Be cooled to room temperature,, filter discharging with 1.21 part of 35% NaOH neutralization.Obtaining 29.81% solid content, average grain diameter is the emulsion (using Malvon particle diameter instrument to record) of 52 nanometers, pH=6.2.
Embodiment 2
In one 1000 milliliters four neck round-bottomed flasks, add 26 parts of (all components amounts to 100 parts, and 1 part is equivalent to 6.7 grams, down together) deionized waters, 4.48 parts of isopropyl alcohols, and under nitrogen atmosphere, be warming up to 82 ℃, drip FeSO4 solution and 3 parts of 20%H of 7.46 part 1% then simultaneously
2O
2Solution and by solution mixture that following component constituted: 32.24 parts of water, 19.40 parts of methylacryoyloxyethyl trimethyl ammonium chlorides (DMC), 11.94 parts of acrylamides.The reinforced time is 4 hours, the reinforced insulation 1 hour that finishes.Under 95 ℃, steam whole isopropyl alcohols then.Be cooled to room temperature and filter discharging.Obtain the polyquaternium dispersant of 30.16% solid content, it is 1860 that gel chromatography (GPC) records weight average molecular weight.
In one 1000 milliliters four neck round-bottomed flasks, (all components amounts to 100 parts to add 36.8 parts, 1 part is equivalent to 7.72 grams, deionized water down together), add polyquaternium dispersant solution, 0.47 part of allyl trimethyl ammonium chloride and 0.79 part of isoamyl alcohol of 11.68 parts of above-mentioned preparations, and under nitrogen atmosphere, be warming up to 85 ℃.Drip 8.55 part 2.0% azo two NSC 18620s then simultaneously and by emulsion-type additive that following component constituted: 16.40 parts of water, 0.18 the softex kw of part, 8.55 parts of butyl acrylates, 4.86 parts of methyl methacrylates, 11.73 part styrene, 0.78 part of acrylamide.The reinforced time is 3 hours; After reinforced being all over, 85 ℃ are incubated 30 minutes down.Be cooled to room temperature, filter discharging.Obtaining 29.72% solid content, average grain diameter is the emulsion (using Malvon particle diameter instrument to record) of 44 nanometers.
Embodiment 3
In one 1000 milliliters four neck round-bottomed flasks, (all components amounts to 100 parts to add 13.8 parts, 1 part is equivalent to 7.24 grams, deionized water, 2.9 parts of isopropyl alcohols down together), and under nitrogen atmosphere, be warming up to 82 ℃, drip 4.83 part 20% sodium peroxydisulfate solution then simultaneously and by solution mixture that following component constituted: 22.8 parts of water, 11.6 parts of maleic anhydrides, 7.73 parts of acrylic acid.The reinforced time is 4 hours, the reinforced insulation 1 hour that finishes.Under 95 ℃, steam whole isopropyl alcohols then.Be cooled to room temperature, the sampling and measuring molecular weight.With 39.23 part of 35% NaOH neutralization, filter discharging.Obtain the polycarboxylate salt dispersant of 29.88% solid content, it is 1520 that gel chromatography (GPC) records weight average molecular weight.
In one 1000 milliliters four neck round-bottomed flasks, (all components amounts to 100 parts to add 34.63 parts, 1 part is equivalent to 7.59 grams, deionized water down together), add polycarboxylate salt dispersant's solution, 0.5 part of allyl sodium phosphate and 0.88 part of isoamyl alcohol of 11.35 parts of above-mentioned preparations, and under nitrogen atmosphere, be warming up to 85 ℃.Drip 6.85 part 2.2% ammonium persulfate solution then simultaneously and by emulsion-type additive that following component constituted: 20.15 parts of water, 0.18 the dodecyl phenol ether sodium sulfate of part, 8.69 parts of butyl acrylates, 4.94 parts of methyl methacrylates, 11.92 part styrene, 0.79 part of acrylic acid.The reinforced time is 3 hours; After reinforced being all over, 85 ℃ are incubated 30 minutes down.Be cooled to room temperature,, filter discharging with 1.21 part of 35% NaOH neutralization.Obtaining 33.23% solid content, average grain diameter is the emulsion (using Malvon particle diameter instrument to record) of 49 nanometers, pH=6.0.
Resulting emulsion of the foregoing description 1-3 and commercially available emulsion surface sizing agent (contrast A) are used contrast, and the result is as follows:
1, the preparation of surface size, dispose glue according to following proportioning:
Starch: 100 parts
Salt: 2 parts
Emulsion surface sizing agent: 2% (the over dry Cypres is to over dry starch) of amount of starch
2, the electro-photographic paper that adopts not applying glue uses the sizing material that is made into above respectively as body paper, carries out applying glue with identical resin added (single face 1g) on homemade simple and easy sizing applicator.After the intact pattern of applying glue carries out drying with identical temperature and time, detect the surface strength of paper, the cobb value.
3, the physical index of sizing material: table 1
| Numbering | 1# | 2# | 3# | 4# | 5# |
| Solid content % | 10 | 10 | 10 | 10 | 10 |
| The pH value | 8.20 | 8.08 | 8.13 | 7.93 | 7.83 |
| Remarks | Embodiment 1 | Embodiment 2 | Embodiment 3 | Contrast A | Blank starch |
4, become the physical index of paper
The monoplanar surface resin added is: 1g/m2
Table 2
| Test item | Surface strength mean value (m/s) | Surface strength value added (m/s) | Surface strength increases multiple | Two sides surface strength poor (m/s) | Deflection mean value (mNm) | Smoothness s | Coob value (g/m 2) |
| Embodiment 1 paper front | 1.18 | 0.98 | 8.2 | 0.18 | 0.14 | 34 | 23.5 |
| Embodiment 1 reverse side of paper | 1.00 | 0.88 | 4.4 | 33 | 23.1 | ||
| Embodiment 2 paper fronts | 1.38 | 1.26 | 10.5 | 0.42 | 0.11 | 33 | 22.3 |
| Embodiment 2 reverse side of paper | 0.96 | 0.76 | 3.8 | 26 | 25.1 | ||
| Embodiment 3 paper fronts | 1.36 | 1.24 | 10.3 | 0.32 | 0.13 | 31 | 27.4 |
| Embodiment 3 reverse side of paper | 1.04 | 0.84 | 4.2 | 25 | 28.8 | ||
| Contrast A paper front | 0.86 | 0.74 | 6.2 | 0.24 | 0.15 | 31 | 30.8 |
| Contrast B reverse side of paper | 0.62 | 0.42 | 2.1 | 28 | 34.2 | ||
| Applying glue body paper front not | 0.12 | -0.08 | 0.13 | 34 | 48.6 | ||
| Applying glue body paper reverse side not | 0.20 | 30 | 41.3 |
5, become the printing adaptability of paper
Table 3 applying glue pattern printability
| Numbering | Field density | 70% site increases | 40% site increases |
| Contrast A | 0.73 | 1％ | 1％ |
| Embodiment 1 | 0.84 | -1％ | 0％ |
From above correction data as can be known, use the prepared embodiment 1-3 of the present invention paper to be carried out top sizing, can increase substantially strength of paper, significantly improve the Cobb value, effectively improve the printing adaptability of smoothness, deflection and paper with starch.
Claims (6)
1, a kind of nano emulsion type surface gluing agent is characterized in that: described nano emulsion type surface gluing agent is to be the C of the allylsulfonate of polycarboxylate salt dispersant, 0.5-50% of 5-20% or allyl phosphate, 0.1-10% by percentage by weight
5---C
8Alcohol, after the additive of 15-60% and the deionized water of 20-40% mix, the NaOH that adds 0.5-1.5% at last neutralizes, the percentage by weight of each component and be 100% in the described Cypres, wherein additive is that the water of one or more and 10-20% of following material mixes: the alkylphenol ether sodium sulfate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, EHMA, styrene, divinylbenzene.
2, a kind of nano emulsion type surface gluing agent according to claim 1, it is characterized in that: described polycarboxylate salt dispersant, be that the sodium peroxydisulfate solution that adds 2-10 part 20% at last makes after being mixed by 10-40 part deionized water, 1-20 part isopropyl alcohol, 5-25 part maleic anhydride and 1-15 part acrylic acid.
3, a kind of nano emulsion type surface gluing agent is characterized in that: described nano emulsion type surface gluing agent is to be the polyquaternium dispersant of 5-20%, the allyl quaternary ammonium salt of 0.5-50%, the C of 0.1-10% by percentage by weight
5---C
8Alcohol, the additive of 15-60% and the deionized water of 20-40% mix, the percentage by weight of each component and be 100% in the described surface additive, wherein additive is that the water of one or more and 10-20% of following material mixes: azo two NSC 18620s, DTAB, softex kw, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, acrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, EHMA, styrene, divinylbenzene.
4, a kind of nano emulsion type surface gluing agent according to claim 3, it is characterized in that: the polyquaternium dispersant, be to be mixed by 10-40 part deionized water, 1-20 part isopropyl alcohol, 10-40 part methylacryoyloxyethyl trimethyl ammonium chloride (DMC), 5-20 part acrylamide, the copperas solution and 1-10 part 20% hydrogen peroxide solution that add 2-10 part 1% again make.
5, a kind of preparation method of nano emulsion type surface gluing agent is characterized in that: the preparation method of described nano emulsion type surface gluing agent is as follows: a, be the deionized water of 20-40%, the polycarboxylate salt dispersant of 5-20%, the allylsulfonate of 0.5-50% or the C of allyl phosphate and 0.1-10% with percentage by weight
5---C
8Alcohol mix the back and under nitrogen environment, be warming up to 80-90 ℃; The additive of b, adding 15-60% is incubated 15-30 minute down at 70-85 ℃, is cooled to room temperature; C, the NaOH that adds 0.5-1.5% at last neutralizes, filter discharging, the percentage by weight of each component and be 100% in the described Cypres, the additive in the b step are that the water of one or more and 10-20% of following material mixes: azo two NSC 18620s, DTAB, softex kw, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, acrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, EHMA, styrene, divinylbenzene.
6, a kind of preparation method of nano emulsion type surface gluing agent is characterized in that: the preparation method of described nano emulsion type surface gluing agent is as follows: a, be the deionized water of 20-40%, the polyquaternium dispersant of 5-20%, the allyl quaternary ammonium salt of 0.5-50% and the C of 0.1-10% with percentage by weight
5---C
8Alcohol mix the back and under nitrogen environment, be warming up to 80-90 ℃; B, the additive that adds 15-60%, be incubated 15-30 minute down at 70-85 ℃, be cooled to room temperature, filter discharging, the percentage by weight of each component and be 100% in the described Cypres, the additive in the b step are that the water of one or more and 10-20% of following material mixes: azo two NSC 18620s, DTAB, softex kw, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, acrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, EHMA, styrene, divinylbenzene.
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| CN102731671B (en) * | 2012-06-29 | 2014-07-16 | 上海东升新材料有限公司 | Modified xanthan gum surface sizing agent, and preparation method thereof |
| CN110894256B (en) * | 2018-09-12 | 2022-03-18 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09111692A (en) * | 1995-10-11 | 1997-04-28 | Seiko Kagaku Kogyo Co Ltd | Sizing agent composition for parermaking |
| CN1225145A (en) * | 1996-05-24 | 1999-08-04 | 赫尔克里士公司 | Sizing composition |
| CN1402805A (en) * | 1999-12-28 | 2003-03-12 | 日本Pmc株式会社 | Surface-sizing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09111692A (en) * | 1995-10-11 | 1997-04-28 | Seiko Kagaku Kogyo Co Ltd | Sizing agent composition for parermaking |
| CN1225145A (en) * | 1996-05-24 | 1999-08-04 | 赫尔克里士公司 | Sizing composition |
| CN1402805A (en) * | 1999-12-28 | 2003-03-12 | 日本Pmc株式会社 | Surface-sizing agent |
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