CN100500995C - Sizing agent for treating paper surface and its preparing method and use - Google Patents

Sizing agent for treating paper surface and its preparing method and use Download PDF

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Publication number
CN100500995C
CN100500995C CNB2006101170240A CN200610117024A CN100500995C CN 100500995 C CN100500995 C CN 100500995C CN B2006101170240 A CNB2006101170240 A CN B2006101170240A CN 200610117024 A CN200610117024 A CN 200610117024A CN 100500995 C CN100500995 C CN 100500995C
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acrylate
methyl
paper surface
sizing agent
monomer
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CN1944792A (en
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施晓旦
王养臣
田久旺
尹东华
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Dssun New Material Shandong Co ltd
Shanghai Dongsheng New Material Co Ltd
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YANZHOU DONGSHENG FINE CHEMICAL CO Ltd
Shanghai Dongsheng New Material Co Ltd
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Abstract

The present invention discloses one kind of paper surface sizing agent and its preparation process and application. The preparation process includes the free radical emulsion polymerization of dispersant, emulsifier, initiator, cationic monomer, (methyl) acrylate monomer and (methyl) styrene monomer at 30-95 deg.c for 2-6 hr. The dispersant is gelatin, and the initiator is persulfate. The paper surface sizing agent has high performance and environment friendship, and when it is used together with starch in sizing paper surface, it can raise the ring pressure strength greatly, improve Cobb value obviously and speed the curing obviously.

Description

A kind of sizing agent for treating paper surface and its production and application
Technical field
The present invention relates to a kind of sizing agent for treating paper surface and its production and application.
Background technology
The development trend of paper, particularly corrugated paper, paperboard shows:
1) just develops to low grammes per square metre direction from high grammes per square metre.
2) adopt waste paper to replace wood pulp, but become the intensity difference of paper, hygroscopicity value height.
3) because the more paper quality instability that causes of internal sizing variable factor, class are difficult to the problem that improves, make manufacturer less with or abandon internal sizing, the technology that the employing top sizing remedies becomes fashion trend.
The sizing agent that is used for above-mentioned top sizing requires: a) improve ring crush intensity; B) significantly reduce Cobb value (hygroscopicity value); C) slaking speed is fast, and machine is just ripe under requiring.
The disclosed a kind of sizing agent of Chinese patent CN1610708A though can reduce the Cobb value, can not obviously improve ring crush intensity, and slaking speed is slow.
Summary of the invention
The objective of the invention is to propose a kind of sizing agent for treating paper surface and its production and application, to overcome the above-mentioned defective that prior art exists.
Sizing agent pH=2 of the present invention~6, solid content 20%~40%, average grain diameter 20nm~50nm, cationic degree 0.02~0.2.
The preparation method of sizing agent for treating paper surface of the present invention comprises the steps:
Dispersant, emulsifying agent, initator, cationic monomer, (methyl) acrylic ester monomer and (methyl) styrene are carried out free-radical emulsion polymerization, and 30 ℃~95 ℃ following reaction time of condition are 2~6 hours;
Said dispersant is a gelatin, and preferable weight-average molecular weight is 10000~100000 gelatin;
Emulsifying agent is CATION and the compound surfactant of nonionic, preferred C 12~18At least a in alkyl polyoxyethylene (n) trimethyl ammonium chloride (n=5~20) can be adopted the commercially available prod, and the trade mark of producing as road, Henan purifying worker technology Co., Ltd is the product of Gemini cationic surfactant 31551;
Initator is a persulfate, is selected from least a in potassium peroxydisulfate, sodium peroxydisulfate or the ammonium persulfate;
Cationic monomer is selected from least a in Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium, Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium, acrylic acid dimethylamino ethyl ester monochloro methane quaternary ammonium, acrylic acid dimethylamino ethyl ester benzyl chloride quaternary ammonium or the diallyldimethylammonium chloride;
(methyl) acrylic ester monomer is selected from 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, acrylic acid-2-ethyl caproite, acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, methacrylic acid-2-Octyl Nitrite, at least a in 2-hydroxyethyl methacry-late or methacrylic acid-2-hydroxypropyl acrylate;
In the technique scheme, by weight percentage:
The consumption of gelatin is 2%~20%, (methyl) cinnamic consumption is 20%~70%, the consumption of cationic monomer is 10%~30%, the consumption of (methyl) acrylic ester monomer is 2%~30%, the consumption of the surfactant that CATION and nonionic are compound is 0.2%~5%, the consumption of persulfate is 0.1%~5%, and adding up to weight is 100%.
Described sizing agent for treating paper surface, the surface treatment that can be used to prepare corrugated paper, paperboard or art post paperboard.
As everyone knows, the stability of the system that the adding polyvinyl alcohol can obviously improve, but the inventor finds effect and not obvious in this system, and it is quite obvious to introduce the gelatin effect.On mechanism, the adhesion of big more prepared aqueous dispersion of cationic degree and fiber is strong more, but the inventor finds that cationic degree surpasses 0.2 o'clock adhesion with fiber and reduces on the contrary, therefore cationic degree must be controlled in 0.02~0.2 the scope, and cationic degree can be controlled by the method for regulating the cationic monomer consumption; The compound emulsifying agent of the CATION of introducing and nonionic lacks than common emulsifier for emulsion polymerization consumption, can obviously reduce the Cobb value.For this aqueous dispersion average grain diameter, the inventor finds fast more in 20nm~50nm slaking speed, and surpassing this scope slaking speed then can be slack-off.
Sizing agent for treating paper surface of the present invention is a kind ofly can satisfy the high-performance that paper for surface sizing uses, the product of environmental protection.This product carries out top sizing with starch to paper, can increase substantially the ring crush intensity of paper, significantly improve the Cobb value, obviously accelerates slaking speed.
The specific embodiment
Embodiment 1
In having the 1000ml four-hole boiling flask of condenser, Dropping feeder, agitator, thermometer, add 5 gram-molecular weights and be 10000 gelatin, 250 gram distilled water are warming up to 85 ℃ of dissolvings.Be cooled to 38 ℃.Adding 100 gram weight concentration is the aqueous solution of 25% octadecyl polyoxyethylene (5) trimethyl ammonium chloride, be heated to 95 ℃, add 25 gram weight concentration, 50% ammonium persulfate aqueous solution, the while Dropwise 50 gram weight concentration 50% Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium aqueous solution and following mix monomer: styrene 175 grams, n-butyl acrylate 20 grams added in 1 hour.In 95 ℃ keep the reaction 1 hour, be cooled to 35 ℃, pH=2.0.Filter through 100 mesh filter screens, get sizing agent for treating paper surface, solid content 39.8%, average grain diameter 20nm (using Malven particle diameter instrument to record), cationic degree 0.13 (adopting the GB12309-90 method to measure).
Embodiment 2
In having the 1000ml four-hole boiling flask of condenser, Dropping feeder, agitator, thermometer, add 20 gram-molecular weights and be 20000 gelatin, 368.4 gram distilled water are warming up to 85 ℃ of dissolvings.Be cooled to 30 ℃.The aqueous solution that adds 0.8 gram, 25% dodecyl polyoxyethylene (20) trimethyl ammonium chloride, the aqueous solution that adds 2 gram weight concentration, 50% potassium peroxydisulfate, drip 60 gram weight concentration, the 50% Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium aqueous solution and following mix monomer simultaneously: methyl styrene 20 grams, EHMA 28.8 grams added in 4 hours.In 30 ℃ keep the reaction 2 hours, be cooled to 25 ℃, pH=5.0.Filter through 100 mesh filter screens, get sizing agent for treating paper surface, solid content 20.1%, average grain diameter 29nm (using Malven particle diameter instrument to record), cationic degree 0.2 (adopting the GB12309-90 method to measure).
Embodiment 3
In having the 1000ml four-hole boiling flask of condenser, Dropping feeder, agitator, thermometer, add 15 gram-molecular weights and be 50000 gelatin, 209.75 gram distilled water are warming up to 85 ℃ of dissolvings.Be cooled to 38 ℃.Add 6 grams, 25% cetyl polyoxyethylene (10) the trimethyl ammonium chloride aqueous solution, be heated to 85 ℃, add 4.5 gram weight concentration, 50% sodium persulfate aqueous solution, drip the cationic monomer aqueous solution and mix monomer simultaneously, added in 2 hours.Wherein, the cationic monomer aqueous solution is made up of 20 gram weight concentration, the 50% Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium aqueous solution and 25 gram weight concentration, the 50% acrylic acid dimethylamino ethyl ester monochloro methane quaternary ammonium aqueous solution; Mix monomer is made up of 63.75 gram styrene and 45 gram methyl methacrylates.In 85 ℃ keep the reaction 1 hour, be cooled to 35 ℃, pH=3.5.Filter through 100 mesh filter screens, get sizing agent for treating paper surface, solid content 29.9%, average grain diameter 40nm (using Malven particle diameter instrument to record), cationic degree 0.02 (adopting the GB12309-90 method to measure).
Embodiment 4
In having the 1000ml four-hole boiling flask of condenser, Dropping feeder, agitator, thermometer, add 10 gram-molecular weights and be 80000 gelatin, 330.63 gram distilled water are warming up to 85 ℃ of dissolvings.Be cooled to 35 ℃.Add 6.4 gram weight concentration, 25% myristyl polyoxyethylene (8) the trimethyl ammonium chloride aqueous solution, be heated to 85 ℃, add 8 gram weight concentration, 50% ammonium persulfate aqueous solution, drip 80 gram weight concentration, the 50% diallyldimethylammonium chloride aqueous solution and following mix monomer simultaneously: methyl styrene 104.4 grams, methyl methacrylate 40 grams added in 2 hours.In 85 ℃ keep the reaction 1 hour, be cooled to 35 ℃, pH=3.5.Filter through 100 mesh filter screens, get sizing agent for treating paper surface, solid content 35.2%, average grain diameter 42nm (using Malven particle diameter instrument to record), CATION 0.07
(adopting the GB12309-90 method to measure).
Embodiment 5
In having the 1000ml four-hole boiling flask of condenser, Dropping feeder, agitator, thermometer, add 15 gram-molecular weights and be 100000 gelatin, 270 gram distilled water are warming up to 75 ℃ of dissolvings.Be cooled to 35 ℃.Add 6 gram weight concentration, 25% myristyl polyoxyethylene (15) the trimethyl ammonium chloride aqueous solution, be heated to 75 ℃, add 1 gram weight concentration, 50% persulfate aqueous solution, drip the cationic monomer aqueous solution and mix monomer simultaneously, added in 2 hours.Wherein, the cationic monomer aqueous solution is made up of 30 gram weight concentration, the 50% diallyldimethylammonium chloride aqueous solution and 20 gram weight concentration, the 50% Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium aqueous solution; Mix monomer is made up of 56 gram styrene and 2 gram methyl acrylates.In 85 ℃ keep the reaction 1 hour, be cooled to 35 ℃, pH=3.5.Filter through 100 mesh filter screens, get sizing agent for treating paper surface, solid content 35.2%, average grain diameter 47nm (using Malven particle diameter instrument to record), cationic degree 0.12 (adopting the GB12309-90 method to measure).
Embodiment 6
In the upper sheet surface applying glue:
The preparation of dextrin: prepare 500 gram weight concentration, the 10% oxidized starch aqueous solution, be warming up to 90 ℃, gelatinization 20 minutes is cooled to 40 ℃, adds the sizing agent of embodiment 1~5 prescription again, again thin up to 8%.
The Cobb pH-value determination pH:
The XSH type of employing Hangzhou Qingtong Boke Automation Technology Co., Ltd. suddenly absorbability analyzer detects pattern to be measured by the GB/T1540-1989 method.
Ring crush intensity is measured:
Adopt the CT300A compressive strength tester of Hangzhou Qingtong Boke Automation Technology Co., Ltd. to detect pattern to be measured.
A) in the applying glue of corrugated paper upper surface:
Use the dextrin of embodiment 1~5 formulated to be coated with the 10# spreading rod on 120 gram corrugated papers, coating weight is 2g/m 2, in 110 ℃ of baking ovens, dried by the fire 30 seconds or 120 seconds respectively after the coating, take out, be cooled to room temperature and measure.
B) in the applying glue of paperboard upper surface:
Use the dextrin of embodiment 1~5 formulated to be coated with the 10# spreading rod on 350 gram paperboards, coating weight is 2g/m 2, in 110 ℃ of baking ovens, dried by the fire 30 seconds or 120 seconds respectively after the coating, take out, be cooled to room temperature and measure.
Figure C200610117024D00071
From above-mentioned application result as can be seen: use the sizing agent of the embodiment of the invention 1~5 preparation, compare, can increase substantially the ring crush intensity of paper, significantly improve the Cobb value, obviously accelerate slaking speed with comparing sample.

Claims (7)

1. the preparation method of a sizing agent for treating paper surface comprises the steps:
Dispersant, emulsifying agent, initator, cationic monomer, (methyl) acrylate monomer and methyl styrene are carried out free-radical emulsion polymerization, and 30 ℃~95 ℃ following reaction time of condition are 2~6 hours, promptly obtain product;
Said dispersant is a gelatin, and initator is a persulfate;
Emulsifying agent is C 12~18At least a in alkyl polyoxyethylene (n) trimethyl ammonium chloride, n is C 12~18The number of repeat unit of alkyl polyoxyethylene, n is 5~20.
2. method according to claim 1 is characterized in that, the weight average molecular weight of gelatin is 10000~100000.
3 methods according to claim 1, it is characterized in that cationic monomer is selected from least a in Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium, Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium, acrylic acid dimethylamino ethyl ester monochloro methane quaternary ammonium, acrylic acid dimethylamino ethyl ester benzyl chloride quaternary ammonium or the diallyldimethylammonium chloride;
(methyl) acrylate monomer is selected from 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, acrylic acid-2-ethyl caproite, acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, methacrylic acid-2-Octyl Nitrite, at least a in 2-hydroxyethyl methacry-late or methacrylic acid-2-hydroxypropyl acrylate.
4. according to each described method of claim 1~3, it is characterized in that, by weight percentage:
Dispersant dosage is 2%~20%, the consumption of methyl styrene is 20%~70%, the consumption of cationic monomer is 10%~30%, the consumption of (methyl) acrylate monomer is 2%~30%, the consumption of emulsifying agent is 0.2%~5%, initiator amount is 0.1%~5%, and adding up to weight is 100%.
5. the sizing agent for treating paper surface of each described method preparation of claim 1~4.
6. sizing agent for treating paper surface according to claim 5 is characterized in that, product pH=2~6, solid content 20%~40%, average grain diameter 20nm~50nm, cationic degree 0.02~0.2.
7. according to the application of claim 5 or 6 described sizing agent for treating paper surface, it is characterized in that, be used to prepare the surface treatment of corrugated paper, paperboard or art post paperboard.
CNB2006101170240A 2006-10-11 2006-10-11 Sizing agent for treating paper surface and its preparing method and use Expired - Fee Related CN100500995C (en)

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Cited By (2)

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CN102797194A (en) * 2011-05-26 2012-11-28 山东贵和显星纸业有限公司 Moisture-proof agent for paper surface and preparation method for moisture-proof agent
CN107338677A (en) * 2017-07-24 2017-11-10 佛山金盛联合纸业有限公司 A kind of corrugated paper Cypres and preparation method thereof

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