CN103334339B - Positive ion styrene-acrylic emulsion surface sizing agent with high reactivity for papermaking and synthetic method thereof - Google Patents
Positive ion styrene-acrylic emulsion surface sizing agent with high reactivity for papermaking and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses a positive ion styrene-acrylic emulsion surface sizing agent with high reactivity for papermaking and a synthetic method thereof. The synthetic method comprises the following steps of: carrying out pre-emulsification on PVA (Polyvinyl Acetate) aqueous solution, a part of hydrophilic monomer, a part of molecular weight modifier and a part of hydrophobicity monomer in a high-speed emulsifier; when the temperature is 75 DEG, dropwise adding an oil-soluble initiating agent and a mixture of the rest of monomers and the rest of molecular weight modifier for 2-4 hours, carrying out heat preservation at 75-80 DEG C, then heating to 80-85 DEG C, dropwise adding a water-soluble initiating agent and a reducing agent for 30-60 minutes, heating to 85-90 DEG C, rapidly adding a quaternization agent, carrying out heat preservation for 1-1.5 hours, reducing the temperature to 45 DEG C, adding organic acid for adjusting pH value to 2-5, sequentially adding a sterilizing agent and a defoaming agent, fully stirring and discharging. The sizing agent disclosed by the invention has the characteristics of a styrene-acrylic emulsion and very good surface sizing capacity due to the high reactivity and the positive ionicity and can endow paper with good water resistance and surface strength.
Description
Technical field
The present invention relates to the sizing agent in paper industry and synthetic method, especially relate to a kind of cationic styrene-acrylic emulsion Cypres and synthetic method of paper grade (stock) high reaction activity.
Background technology
Secondary stock is a kind of Papermaking Resource taking into account economic benefit and social benefit, is subject to the common concern of countries in the world.Utilize secondary stock production high-strength corrugated paper or the primary slurry of Substitute For Partial to produce Cultural Paper to be approved widely.The principal element affecting secondary fibers newspaper printability has Fundamental Physical Properties, optical property, mechanical property, absorbability etc.Good printability can not only ensure that printing is carried out smoothly, and can better ensure printing quality.Top sizing improves the more effective approach of paper printing adaptability, its printing performance can be improved by carrying out top sizing to paper and paperboard, increase its surface strength, certain repellence is had to its hair and powder dropping, improve its internal bond strength, folding strength, IGT picking strength, increase its deflection, smoothness, reduces its air permeability, and improves the paper oil resistant of resistance to fat or water repelling property etc.Top sizing is also one of important method significantly improving paper added value.
Auxiliary agent is added in top sizing process contrast, retention is close to 100%, and directly act on paper surface, overcome that the such as paper machine that interior interpolation auxiliary agent exists pollutes, bubbles, high temperature is manufactured paper with pulp the low inferior sequence of operations sex chromosome mosaicism of degree of sizing, the development trend of the variation of mode of printing, high speed and paper products high-quality can be adapted to.Traditional starch surface sizing agent due to the affinity of itself and fiber poor, the continuous evaporation of moisture and the continuous contraction of rete cover starch film on paper in dry run along with there will be film rupture phenomenon, therefore in printing process, easily there is the phenomenons such as hair and powder dropping, and synthetic surface sizing agent is character according to paper fibre and feature, adopt the polymerization single polymerization monomer with difference in functionality, be prepared from certain technique and ratio polymerization.Compared with starch, the affinity between this base polymer and fiber is higher.At present at paper industry, synthetic surface sizing agent and oxidized starch or enzyme starch complex can be applied by top sizing application usually.Synthetic surface sizing agent is day by day subject to paper-making industry and payes attention to, and is owing to using wastepaper as raw material and mineral filler in a large number on the one hand, needs the surface property improving and improve paper; Then on the other hand meet that paper products become more diverse, the requirement of high added value.
Synthetic surface sizing agent is a kind of Cypres with several functions, and formed with suitable ratio copolymerization by the multiple activated monomer with various function, gained chemicals can change the inherent characteristic of paper potentially.Along with developing rapidly of high speed printing technology, having multi-functional polymer Surface Sizing Agent very fast at world's scales, is the main product of current Cypres.Polymer Surface Sizing Agent mainly can be classified three types: (1) water-soluble polymer Cypres (SMA and SAA); (2) aqueous polymer dispersion Cypres (SAE class); (3) polyurethane aqueous dispersion Cypres (PUD class).Synthetic surface sizing agent has extraordinary film forming, and the film formed has good plasticity, obviously can reduce the hair and powder dropping phenomenon in paper printing process, and provides a good surface for coating operations.Therefore can prevent the infiltration that ink is excessive compared with traditional Cypres, to alleviate print through phenomenon, thus reach the object improving printing quality.According to document introduction, way popular abroad reduces paper internal sizing amount at present, strengthen top sizing to the ornamenting effect of paper surface, thus make paper while the good applying glue of acquisition, also improve its stiff degree, planarization and increase surface strength and reduce page distortion.
US Patent No. 6802939 B1 discloses with the oligomer of acrylamide/MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride as emulsifying agent, and then obtain cation surface sizing agent with styrene/acrylic 2-Octyl Nitrite for monomer carries out polymerization, although the stability of this polymer is better, but polyacrylamide is hydrophilic, perhaps because the reason of technical know-how, Surface Sizing Properties is worth reauthentication.
US Patent No. 4855343 discloses with enzyme starch as carrier, be that monomer carries out copolymerization with the acrylate of (methyl) acrylonitrile, C3-C8, obtain Cypres, this polymer has good stability and Surface Sizing Properties, and cost is low, mechanical resistant performance is good.
It is the method that carrier carries out being polymerized that above patent all provides with low polymer, the polymerization of PVA many application anion form surface sizing agent simultaneously, although relevant PVA is had for the document of cation surface sizing agent domestic, but because the hydrophily of PVA has influence on the effect of top sizing, there is no relevant patent.
Summary of the invention
The object of the present invention is to provide a kind of cationic styrene-acrylic emulsion Cypres and synthetic method of paper grade (stock) high reaction activity, solving existing employing PVA-1788 or PVA-1799 is that emulsifier WATER RESISTANCE that is many and PVA is poor, cation group in polymer also has stronger hydrophily, thus make obtained Cypres WATER RESISTANCE not enough and the problem of industrial applications cannot be reached, solve the problems such as the stability of the Cypres with reactivity, mechanical resistant and foaminess simultaneously.
For achieving the above object, the technical solution used in the present invention is as follows:
One, a cationic styrene-acrylic emulsion Cypres for paper grade (stock) high reaction activity, the percentage by weight of each component is:
Water 50-70%
Hydrophobic monomer 7-35%
Hydrophilic monomer 2-8%
PVA 1-6%
Oil-soluble initiator 0.05-0.15%
Molecular weight regulator 0.02-0.15%
Organic acid 1.5-4%
Water soluble starter 1-5%
Water-soluble reducing agent 0-0.2%
Silicone defoaming agent 0.01-0.05%
Quaternizing agent 0-6%
Isothiazolinone 0.002-0. 01%.
Two, a synthetic method for the cationic styrene-acrylic emulsion Cypres of paper grade (stock) high reaction activity, the step of the method is as follows:
(1) prepare burden: the percentage by weight of each component is:
Water 50-70%, hydrophobic monomer 7-35%, hydrophilic monomer 2-8%, PVA 1-6%, oil-soluble initiator 0.05-0.15%, molecular weight regulator 0.02-0.15%, organic acid 1.5-4%, water soluble starter 1-5%, water-soluble reducing agent 0-0.2%, silicone defoaming agent 0.01-0.05%, quaternizing agent 0-6%, isothiazolinone disinfecting agent 0.002-0. 01%;
(2) pre-emulsification: by PVA 1-6% and the water-soluble 40-60% of hydrophilic monomer 0-3%, obtain the homogeneous aqueous solution containing PVA, hydrophilic monomer 2-5%, hydrophobic monomer 7-35% and molecular weight regulator 0.02-0.15% are mixed into homogeneous monomer mixed solution, being joined by monomer mixed solution homogeneous for 25-45wt% in the aqueous solution containing PVA adopts emulsify at a high speed device to carry out pre-emulsification, emulsifying temperature is 65-70 DEG C, obtains pre-emulsification monomer mixed solution;
(3) emulsion polymerisation: under stirring, pre-emulsification monomer mixed solution is warming up to 75-80 DEG C, drip the monomer mixed solution of oil-soluble initiator 0.05-0.15% and 55-75wt% simultaneously, time for adding is 2-4 hour, holding temperature is 75-80 DEG C, then 80-85 DEG C is warming up to, drip water soluble starter 1-5% and water-soluble reducing agent 0-0.2% simultaneously, time for adding is 30-60 minute, in 10 minutes, quaternizing agent 0-6% is dripped immediately after dropping terminates, be warming up to 85-90 DEG C of insulation 1-1.5 hour again, organic acid 1.5-4% is added after being cooled to 45 DEG C, adjust ph is to 2-5, and add isothiazolinone disinfecting agent 0.002-0. 01% and silicone defoaming agent 0.01-0.05% and remaining water successively, discharging after abundant stirring.
Described hydrophobic monomer is styrene and butyl acrylate, styrene and methyl methacrylate, styrene and propylene 2-Octyl Nitrite, methyl styrene and butyl acrylate, methyl styrene and methyl methacrylate, more than methyl styrene and propylene 2-Octyl Nitrite in two kinds of combinations, get any one group, both arbitrary proportions mixing in any a group.
Described hydrophilic monomer is one or more arbitrary proportions mixing in dimethylaminoethyl acrylate methyl ammonia ethyl ester, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride.
Described PVA is one or more arbitrary proportions mixing in PVA-0388, PVA-0488, PVA-0588, PVA-0788, PVA-0888, PVA-0399, PVA-0499, PVA-0599, PVA-0799, PVA-0899.
Described oil-soluble initiator is one or both arbitrary proportions mixing in azodiisobutyronitrile, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, the own ester of di-tert-butyl peroxide.
Described water soluble starter is the one in aqueous hydrogen peroxide solution, ammonium persulfate, potassium peroxydisulfate, azo diisobutyl imidazoline hydrochloride, azo-bis-isobutyrate hydrochloride; Described water-soluble reducing agent is the one in frerrous chloride, ferrous sulfate, organic amine.
Described molecular weight regulator is the one in n-dodecyl mereaptan, tert-butyl group lauryl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, mercaptoethanol.
Described quaternizing agent is the one in benzyl chloride, epoxychloropropane, dimethyl suflfate; Described organic acid is one in formic acid, acetic acid, citric acid or or two kinds of arbitrary proportions mixing.
Compared with background technology, the beneficial effect that the present invention has is:
1, the present invention adopts low-molecular-weight PVA, overcomes high molecular PVA-1788 and PVA-1799 and needs long-time dissolving and the easy shortcoming producing gel.
2, the low-molecular-weight PVA consumption of the present invention's employing is less, and reactive grafting is effective, and emulsion still can be kept to have good stability.
3, present invention efficiently solves PVA can bring WATER RESISTANCE deficiency problem to Cypres, make this Cypres have high reactivity by a series of reaction.
4, the present invention is by controlling the composition of hydrophilic monomer and ionic state, and when keeping and control pre-emulsification, the stability of emulsion and final product emulsion, ensure that the effect of Cypres simultaneously.
5, the present invention adopts the mode that oil-soluble initiator combines with water soluble starter, effectively improves the polymerization between monomer.
6, the present invention solves the stability problem of the Cypres with reactivity by organic acid application, can reach suitability for industrialized production and application.
7, the present invention substantially increases the surface strength of paper, reduces hair and powder dropping, effectively can also improve the degree of sizing of paper, smoothness and printability.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, but the embodiment of the present invention is not limited thereto.
embodiment 1:
Take 2.00 grams of PVA-0788 and 2.00 gram PVA-0399 and be dissolved in heating fully dissolving in 150 grams of distilled water, become transparent colloidal solution A, now fluid temperature is 70-75 DEG C.Take 50 grams of styrene, 27 grams of 2-EHAs, 20 grams of dimethylaminoethyl acrylate methyl ammonia ethyl esters, 4 grams of acrylyl oxy-ethyl-trimethyl salmiacs respectively, after 2 grams of n-dodecyl mercaptans fully mix, the mixed material getting 30wt% adds in colloidal solution and carries out emulsify at a high speed, obtains emulsion B.Separately taking 0.5 gram of dibenzoyl peroxide is dissolved in 8 grams of ethanol, is oil-soluble initiator C.Drip the mixed material of oil-soluble initiator C and residue 70wt% respectively in 75-80 DEG C, time for adding is 2 hours.Then adding water-soluble reducing agent concentration is 1% ferrous chloride aqueous solution 5 grams, and to start after the material in reactor is warming up to 80-85 DEG C to drip concentration be 2% hydrogen peroxide initator 30 grams, time for adding is 30 minutes, after hydrogen peroxide dropwises, add quaternizing agent epoxychloropropane fast immediately and be warming up to 85-90 DEG C of insulation 1 hour until emulsion by white to blueing light, overall display oyster white.Adding formic acid adjust ph after being cooled to 45 DEG C is 2-5, then adds a small amount of silicone defoaming agent and isothiazolinone disinfecting agent fully stirs rear discharging, obtains sample 1#.
embodiment 2:
Take 18.5 grams of PVA-0588 and 5 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and be dissolved in heating fully dissolving in 150 grams of distilled water, become transparent colloidal solution A, now fluid temperature is 70-75 DEG C.Take 50 grams of methyl styrenes respectively, after 30 grams of butyl acrylates, 1.5 grams of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 1.5 grams of tertiary lauryl mercaptans fully mix, the mixed material getting 30wt% adds in colloidal solution and carries out emulsify at a high speed, obtains emulsion B.Separately taking 0.5 gram of azodiisobutyronitrile is dissolved in 10 grams of acetone, is oil-soluble initiator C.Drip the mixed material of oil-soluble initiator C and residue 70wt% respectively in 75-80 DEG C, time for adding is 2 hours.Then adding water-soluble reducing agent concentration is 1% ferrous sulfate aqueous solution 5 grams, and to start after the material in reactor is warming up to 80-85 DEG C to drip concentration be 1% ammonium persulfate initiator 30 grams, time for adding is 30 minutes, after ammonium persulfate aqueous solution dropwises, be warming up to 85-90 DEG C of insulation 1 hour until emulsion by white to blueing light, overall display oyster white.Adding formic acid adjust ph after being cooled to 45 DEG C is 2-5, then adds a small amount of silicone defoaming agent and isothiazolinone disinfecting agent fully stirs rear discharging, obtains sample 2#.
embodiment 3:
Take 8.00 grams of PVA-0488 and 5 gram dimethyl diallyl ammonium chlorides and be dissolved in heating fully dissolving in 120 grams of distilled water, become transparent colloidal solution A, now fluid temperature is 70-75 DEG C.Take 60 grams of methyl styrenes, 35 grams of 2-EHAs, 5 grams of dimethylaminoethyl acrylate methyl ammonia ethyl esters respectively, after 3 grams of mercaptoethanols fully mix, the mixed material getting 40wt% adds in colloidal solution and carries out emulsify at a high speed, obtains emulsion B.Separately taking 0.5 gram of own ester of di-tert-butyl peroxide is dissolved in 10 grams of isopropyl alcohols, is oil-soluble initiator C.Drip the mixed material of oil-soluble initiator C and residue 60wt% respectively in 75-80 DEG C, time for adding is 2 hours.Then adding water-soluble reducing agent concentration is the 1% diethanol amine aqueous solution 5 grams, and to start after the material in reactor is warming up to 80-85 DEG C to drip concentration be 2% azo diisobutyl amidine hydrochloride initator 30 grams, time for adding is 30 minutes, add quaternizing agent benzyl chloride fast immediately after dropwising and be warming up to 85-90 DEG C of insulation 1 hour until emulsion by white to blueing light, overall display oyster white.Adding mixed acid (formic acid: citric acid=3:1) adjust ph after being cooled to 45 DEG C is 2-5, then adds a small amount of silicone defoaming agent and isothiazolinone disinfecting agent fully stirs rear discharging, obtains sample 3#.
embodiment 4:
Take 18.00 grams of PVA-0388 and be dissolved in heating fully dissolving in 180 grams of distilled water, become transparent glue A, now fluid temperature is 70-75 DEG C.Take 25 grams of styrene, 20 grams of methyl methacrylates, 24g dimethylaminoethyl acrylate methyl ammonia ethyl esters respectively, after 1.5 grams of 2,4-diphenyl-4-methyl-1-pentenes fully mix, the mixed material getting 20wt% adds in colloidal solution and carries out emulsify at a high speed, obtains emulsion B.Separately taking 0.5 gram of di-isopropyl peroxydicarbonate is dissolved in 10 grams of isopropyl alcohols, is oil-soluble initiator C.Drip the mixed material of oil-soluble initiator C and residue 80wt% respectively in 75-80 DEG C, time for adding is 2 hours.Then adding water-soluble reducing agent concentration is the 1% diethanol amine aqueous solution 5 grams, and to start after the material in reactor is warming up to 80-85 DEG C to drip concentration be 2% azo diisobutyl imidazoline hydrochloride initator 30 grams, time for adding is 30 minutes, add quaternizing agent dimethyl suflfate fast immediately after dropwising and be warming up to 85-90 DEG C of insulation 1 hour until emulsion by white to blueing light, overall display oyster white.Adding mixed acid (formic acid: acetic acid=1:1) adjust ph after being cooled to 45 DEG C is 2-5, then adds a small amount of silicone defoaming agent and isothiazolinone disinfecting agent fully stirs rear discharging, obtains sample 4#.
application test and effect assessment:
Carry out composite with the samples of latex of synthesizing in embodiment and starch respectively, coating sizing test machine carries out base paper sheet face applying glue application test.
Applying glue body paper used is be quantitatively 70g/m
2cultural Paper body paper, correlated performance detect as following table 1:
Table 1 body paper performance test results
| Quantitatively (g/ ㎡) | 60s Cobb value (g/ ㎡) | Surface strength (m/s) | Smoothness (s) |
| 68～72 | 110.1 | 0.82 | 16.2 |
Prepare the test parameters of starch glue application solution: the concentration of cassava oxidized starch liquid is 5 ~ 10%, the mass ratio of emulsion of the present invention and cassava oxidized starch is 1 ~ 5:10, and the PH scope of coating fluid is 3 ~ 5.Applying glue temperature is 60 ~ 70 DEG C, and baking temperature is 65 ~ 105 DEG C, and coating fluid resin added is 120 g/m
2.Rotary dryer is adopted to carry out drying after applying glue.
According to above-mentioned applying glue technique for applying parameter, adopt synthetic sample preparation glue application solution to carry out applying glue application to body paper respectively, after detection applying glue, the correlated performance of paper is as following table 2:
Paper performance testing result after table 2 applying glue
| Quantitatively (g/ ㎡) | 60s Cobb value (g/ ㎡) | Surface strength (m/s) | Smoothness (s) |
| 70.5～75 | 32.6～30.8 | 0.85～1.27 | 18.3～20.3 |
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to allow the professional being familiar with technique can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (8)
1. a synthetic method for the cationic styrene-acrylic emulsion Cypres of paper grade (stock) high reaction activity, is characterized in that, the step of the method is as follows:
(1) prepare burden: the percentage by weight of each component is:
Water 50-70%, hydrophobic monomer 7-35%, hydrophilic monomer 2-8%, PVA 1-6%, oil-soluble initiator 0.05-0.15%, molecular weight regulator 0.02-0.15%, organic acid 1.5-4%, water soluble starter 1-5%, water-soluble reducing agent 0-0.2%, silicone defoaming agent 0.01-0.05%, quaternizing agent 0-6%, isothiazolinone disinfecting agent 0.002-0. 01%;
(2) pre-emulsification: by PVA 1-6% and the water-soluble 40-60% of hydrophilic monomer 0-3%, obtain the homogeneous aqueous solution containing PVA, hydrophilic monomer 2-5%, hydrophobic monomer 7-35% and molecular weight regulator 0.02-0.15% are mixed into homogeneous monomer mixed solution, being joined by monomer mixed solution homogeneous for 25-45wt% in the aqueous solution containing PVA adopts emulsify at a high speed device to carry out pre-emulsification, emulsifying temperature is 65-70 DEG C, obtains pre-emulsification monomer mixed solution;
(3) emulsion polymerisation: under stirring, pre-emulsification monomer mixed solution is warming up to 75-80 DEG C, drip the monomer mixed solution of oil-soluble initiator 0.05-0.15% and 55-75wt% simultaneously, time for adding is 2-4 hour, holding temperature is 75-80 DEG C, then 80-85 DEG C is warming up to, drip water soluble starter 1-5% and water-soluble reducing agent 0-0.2% simultaneously, time for adding is 30-60 minute, in 10 minutes, quaternizing agent 0-6% is dripped immediately after dropping terminates, be warming up to 85-90 DEG C of insulation 1-1.5 hour again, organic acid 1.5-4% is added after being cooled to 45 DEG C, adjust ph is to 2-5, and add isothiazolinone disinfecting agent 0.002-0. 01% and silicone defoaming agent 0.01-0.05% and remaining water successively, discharging after abundant stirring.
2. the synthetic method of the cationic styrene-acrylic emulsion Cypres of a kind of paper grade (stock) high reaction activity according to claim 1, it is characterized in that: described hydrophobic monomer is styrene and butyl acrylate, styrene and methyl methacrylate, styrene and 2-ethylhexyl acrylate, methyl styrene and butyl acrylate, methyl styrene and methyl methacrylate, more than methyl styrene and 2-ethylhexyl acrylate in two kinds of combinations, get any one group, both arbitrary proportions mixing in any a group.
3. the synthetic method of the cationic styrene-acrylic emulsion Cypres of a kind of paper grade (stock) high reaction activity according to claim 1, is characterized in that: described hydrophilic monomer is one or more arbitrary proportions mixing in dimethylaminoethyl acrylate methyl ammonia ethyl ester, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride.
4. the synthetic method of the cationic styrene-acrylic emulsion Cypres of a kind of paper grade (stock) high reaction activity according to claim 1, is characterized in that: described PVA is one or more arbitrary proportions mixing in PVA-0388, PVA-0488, PVA-0588, PVA-0788, PVA-0888, PVA-0399, PVA-0499, PVA-0599, PVA-0799, PVA-0899.
5. the synthetic method of the cationic styrene-acrylic emulsion Cypres of a kind of paper grade (stock) high reaction activity according to claim 1, is characterized in that: described oil-soluble initiator is one or both arbitrary proportions mixing in azodiisobutyronitrile, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, the own ester of di-tert-butyl peroxide.
6. the synthetic method of the cationic styrene-acrylic emulsion Cypres of a kind of paper grade (stock) high reaction activity according to claim 1, is characterized in that: described water soluble starter is the one in aqueous hydrogen peroxide solution, ammonium persulfate, potassium peroxydisulfate, azo diisobutyl imidazoline hydrochloride, azo-bis-isobutyrate hydrochloride; Described water-soluble reducing agent is the one in frerrous chloride, ferrous sulfate, organic amine.
7. the synthetic method of the cationic styrene-acrylic emulsion Cypres of a kind of paper grade (stock) high reaction activity according to claim 1, it is characterized in that: described molecular weight regulator is the one in n-dodecyl mereaptan, tert-butyl group lauryl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, mercaptoethanol.
8. the synthetic method of the cationic styrene-acrylic emulsion Cypres of a kind of paper grade (stock) high reaction activity according to claim 1, is characterized in that: described quaternizing agent is the one in benzyl chloride, epoxychloropropane, dimethyl suflfate; Described organic acid is one or both arbitrary proportions mixing in formic acid, acetic acid, citric acid.
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| CN110747688B (en) * | 2019-10-14 | 2023-03-24 | 浙江理工大学 | Mineral oil emulsion stripping agent composition for papermaking dryer and preparation method thereof |
| CN111608010B (en) * | 2020-04-17 | 2021-12-31 | 仙鹤股份有限公司 | Preparation method of high-strength low-static CTP lining paper |
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| CN101568687A (en) * | 2006-12-20 | 2009-10-28 | 巴斯夫欧洲公司 | Mixtures of paper gluing agents |
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| DE3537824A1 (en) * | 1985-10-24 | 1987-04-30 | Bayer Ag | CATIONIC SIZE FOR PAPER |
| CN101568687A (en) * | 2006-12-20 | 2009-10-28 | 巴斯夫欧洲公司 | Mixtures of paper gluing agents |
| CN103105751A (en) * | 2012-12-27 | 2013-05-15 | 深圳市乐普泰科技股份有限公司 | Preparation method of suspension polymerization powdered ink with core-shell structure |
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