CN1109489A - Method for preparation of disperser used in glue applying agent and aqueous emulsion - Google Patents
Method for preparation of disperser used in glue applying agent and aqueous emulsion Download PDFInfo
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- CN1109489A CN1109489A CN 94103908 CN94103908A CN1109489A CN 1109489 A CN1109489 A CN 1109489A CN 94103908 CN94103908 CN 94103908 CN 94103908 A CN94103908 A CN 94103908A CN 1109489 A CN1109489 A CN 1109489A
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Abstract
The dispersing agent for sizing agent consists of water soluble high molecular compound which is obtained by graft polymerization of alkaline salt of styrol/acrylic acid or methyl olefine acid polymer and acrylamide or methyl acrylamide. The sizing agent is prepared from the mixture of hydrophobic resins and petroleum resins, abietic ester compound, additive compound of alpha, beta unsaturted polyacid through dispersion by the above mentioned disperser and cationizing petroleum resin.
Description
Can have new dispersion agent good sizability, that sizing agent is used in the present invention relates to from acid range to neutral range and from acid range to neutral range in have the new preparation method of the sizing agent of good sizability.
Past, can be used as the sizing agent that in neutral range, uses, can use alkyl ketene dimer system (AKD system), alkenyl succinic anhydrides system (ASA system), perhaps the cationic size of fatty acid series, resin system is main with AKD system and ASA particularly.Report is arranged recently, and the ternary that will make by rosin based with by C, H, O or the rosin esterification thing of tetravalent alcohol carry out the neutral paper-making sizing method (special fair 3-79480 communique) of dispersive.But, recirculation along with waste water, the high speed of paper machine, for ASA system, owing to its pollution that adds the paper machine that the water decomposition thing causes just becomes problem, and for AKD system, it is late that its degree of sizing begins, for example, during the top sizing application job, imbibition control difficulty, and paper is sliding etc., and and ASA system have equally owing to add the problems such as pollution of the paper machine that the water decomposition thing causes, and, in acidity, neutral mixing paper machine, when it is changed, need cleaning system inside or filler problem, and the aspects such as color emissivity of fluorescent coating all there is problem.
Therefore, still the expectation have a kind of in neutral range its effective anionic property sizing agent.
The present inventor, in view of the above problems, studied the strong problem of being concerned about of papermaking industry repeatedly, under the situation as lyophobic dust at rosin derivative or petroleum resin, sizability depends on the kind of the dispersion agent of this lyophobic dust greatly, and dispersion agent is studied.Found that, in normally used in the past water-soluble polymer or the tensio-active agent, in pH is acid range below 6, can obtain sizability, but in the neutrality and even alkaline range of pH value 6～8, all can not expect to have sizability, particularly, in raw material, use CaCO
3Perhaps contain CaCO
3Waste paper when mixing as filler, then can not obtain sizability fully.
Therefore, the invention provides a kind of sizing agent that can have good sizability in from acid range to neutral range with dispersion agent and new preparation method with sizing agent of this performance.
The present inventor is based on above-mentioned opinion, studied repeatedly and used the dispersion agent as base-material such as rosin derivative, petroleum resin, can bring into play sizing agent good sizability, new in the pH value that found that at wide region with dispersion agent and the preparation method that uses the new sizing agent of this dispersion agent, and the preparation method of the sizing agent of making by the new combination of rosin derivative and dispersion agent, and finished the present invention.
That is to say that new dispersion agent of the present invention is to be the NH of the mass polymer of 30000～80000 styrene/acrylic or styrene/methacrylic acid with molecular weight
4, Na or K salt and/or alkanolamine salt constitute with the water-soluble polymer of acrylamide or Methacrylamide graft polymerization.
In addition, use the preparation method of the new sizing agent of new dispersion agent of the present invention, be by in 100 parts of weight of rosin of rosin or the unsaturated polyprotonic acid addition of α, β, 20～60 parts of weight of petroleum resin of mixing petroleum resin or the unsaturated polyprotonic acid addition of α, β, and use water-soluble polymer dispersant of the present invention to disperse the mixture of gained and the step that obtains water emulsion constitutes.
Use the preparation method of the new sizing agent of other dispersion agent of the present invention, be by in rosin or the unsaturated polyprotonic acid addition of α, β rosin, carry out esterification with polyvalent alcohol, obtain its acid number (following sometimes claim " AV ") and be 5～100 carboxylate, and it is this carboxylate is independent, the perhaps mixture of forming by 100 parts of weight of this carboxylate and rosin or 20～70 parts of weight of the unsaturated polyprotonic acid addition of α, β rosin, use water-soluble polymer dispersant of the present invention to disperse, constitute with the step that obtains water emulsion.
A preparation method who uses the new sizing agent of dispersion agent of the present invention is arranged again, be by rosin is carried out esterification with polyvalent alcohol, in being 5～50 carboxylate, the acid number of gained adds the unsaturated polyprotonic acid of α, β then, and use water-soluble polymer dispersant of the present invention to disperse the affixture of gained, constitute with the step that obtains water emulsion.
The preparation method of the new sizing agent that constitutes by new combination of the present invention, by at rosin or α, carry out esterification with polyvalent alcohol in the unsaturated polyprotonic acid addition of the β rosin, obtain acid number and be 5～100 carboxylate, then with this carboxylate separately or by 100 parts of weight of this carboxylate and rosin or α, the mixture that 20～70 parts of weight of the unsaturated polyprotonic acid addition of β rosin are formed, use the cationization petroleum resin, cationization rosin or cats product are as dispersion agent, and add tween as required again and disperse, constitute with the step that obtains water emulsion.
The preparation method of another new new sizing agent that constitutes of the present invention carries out esterification with rosin with polyvalent alcohol, in being 5～50 carboxylate, the acid number that obtains adds the unsaturated polyprotonic acid of α, β, then with the affixture of gained, with positively charged ion petroleum resin, cationization rosin or cationic active agent as dispersion agent, and as required, further add tween and disperse, constitute with the step that obtains water emulsion.
The sizing agent that method produced according to the present invention obtains, when being filler particularly as with lime carbonate or the neutrality that contains under the situation of waste paper of lime carbonate of use copy in the slurry, with the neutrality in past copy the slurry identical, use the method for a small amount of Tai-Ace S 150, poly aluminium chloride (PAC) etc. just can bring into play good sizability simultaneously.Method of the present invention replaces above-mentioned rosin esterification thing (special fair 3-79480 communique) with as lyophobic dust the time with petroleum resin, also can obtain obtaining identical effect with this rosin esterification thing, sees it also is very favorable from this point.The sizing agent that the method according to this invention obtains, very low in the foaminess of copying when slurry, be not only aspect sizability, and copy on the slurry also very favourable aspect the problematic foaminess.
Also have, as required, in dispersion agent of the present invention, can and use non-ionic type, aniorfic surfactant.And, also can equally and use protective colloid.
Solvent mode, transform mode of conventional techniques etc. are arranged in the latex method of Shi Yonging in the method for the invention.
Dispersion agent of the present invention is by the NH with the mass polymer of styrene/acrylic or methacrylic acid (AV=150～300)
4, Na or K salt and/or alkanolamine salt, use acrylamide or Methacrylamide to carry out graft polymerization and obtain.Graft polymerization also can and be used propylene ester or methacrylic ester as required in this acid amides.
In the polymerization of making dispersion agent of the present invention, following method is for example arranged.That is to say,, after 1～2 hour, be cooled to 70 ℃～80 ℃, then, use the mass polymerization device, carry out 8 hours polyreactions at 130 ℃～140 ℃ 100 ℃～120 ℃ prepolymerizations with vinylbenzene and vinylformic acid or methacrylic ester.For the acid number of the polymkeric substance of gained, with the NH that makes it to obtain normal ammoniacal liquor etc.
4, Na or K salt and/or the needed alkali number of alkanolamine neutralize, then it is used acrylamide or 30～70 parts of weight of Methacrylamide (the 100 parts of weight of basic salt with the polymkeric substance that obtains are benchmark), preferably use 50 parts of weight, and the interpolation polymerizing catalyst, carry out reaction in 5 hours at 50 ℃～80 ℃.In addition, as required, also can and with acrylate or 5～10 parts of weight of methacrylic ester.
Operable in the present invention rosin has resin, wood rosin, tolu rosin, staybelite etc.
The petroleum resin of Shi Yonging are in the present invention, will pay the C of product when petroleum naphtha decomposes
5Cut and C
9Cut, with Friedel-Crafts catalyst carry out polymeric, softening temperature is 30 ℃～120 ℃, bromine number is 20～100 material, and preferably softening temperature is that 50 ℃～80 ℃, bromine number are 40～60 material.
The unsaturated polyprotonic acid of the α of Shi Yonging, β has toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid etc. in the present invention.
Operable tensio-active agent in the preparation of sizing agent of the present invention, can use the conventional surfactants of anionic, non-ionic type, but best in anionic, can enumerate polyoxyethylene distyryl phenol sulphur sodium succinate, polyoxyethylene triphenylethylene phenol sulphur sodium succinate etc. are arranged, in addition, in the nonionic surface active agent, that can enumerate has polyoxyethylene distyryl phenol, a polyoxyethylene triphenylethylene phenol etc.
In addition, operable protective colloid in the preparation of sizing agent of the present invention, that can enumerate has polyvinyl alcohol (PVA), polyacrylamide (PAM), methylcellulose gum (MC), carboxymethyl cellulose (CMC), starch, a caseic basic salt (NH
4, K, Na), natural gum etc.
In the preparation method of sizing agent of the present invention, the lyophobic dust that uses is rosin or the rosin of the unsaturated polyprotonic acid addition of α, β and the carboxylate of polyvalent alcohol, the rosiny mixture of this carboxylate and rosin or α, the unsaturated polyprotonic acid addition of β or rosin and in the carboxylate of polyvalent alcohol, added under the situation of affixture of α, the unsaturated polyprotonic acid of β, the water emulsion that uses cationic dispersing agent then to obtain in this lyophobic dust has very good sizability.
Here, rosin or α, the rosin of the unsaturated polyprotonic acid addition of β and the carboxylate of polyvalent alcohol can make by habitual esterification, and its acid number is 5～100 material for well, are 5～50 material and be more preferably acid number.
In the present invention, the polyvalent alcohol that uses for esterified rosin etc. has glycerine, trihydroxymethyl propane, tetramethylolmethane etc., and best be glycerine.
In addition, the rosiny blending ratio of above-mentioned carboxylate and rosin or α, the unsaturated polyprotonic acid addition of β is: in 100 parts of weight of carboxylate, its rosin or α, the unsaturated polyprotonic acid addition of β rosin with 20～70 parts of weight for well.
The carboxylate of above-mentioned rosin and polyvalent alcohol also can make by habitual esterification, and to have acid number be 5～50 material for well, is 5～20 material and be more preferably the acid number that has.
In above-mentioned cationic dispersing agent, cationization petroleum resin, cationization rosin or cats product etc. are arranged.For example have, after in petroleum resin, adding the unsaturated polyprotonic acid of α, β, carry out the polyalkylene polyamine reaction, then benzyl muriate, chloroethanol, mineral acid, organic acid reaction and the water-soluble cationic fossil oleo-resinous that obtains and dispersion agent (for example, opening flat 4-93329 communique) with reference to the spy.
In addition; in the preparation of the sizing agent of making by the new combined method of rosin derivative of the present invention and dispersion agent; as required; can and disperse with tween, cationic active agent; and; if desired, as protective colloid, also can and use cationic starch, PVA, PAM, MC etc.
Enumerate suitable embodiment below further describing, but scope of the present invention is not limited to these." part " of using among the embodiment is represented by weight.
The manufacturing of dispersion agent
Production Example-1(anionic)
In reactor, pack into 21.8 parts in 78.2 parts of vinylbenzene and vinylformic acid, under agitation slowly heat up, after 100 ℃～120 ℃ reactions 1.5 hours, reactive system inside is cooled to 70 ℃, pack into immediately then in the polymerization ware, and reacted 8 hours at 130 ℃～140 ℃.
With the polymkeric substance cooling that obtains after the reaction end, and pulverize.Then, in 7.5 parts in the polymkeric substance and 30 parts of emulsification stills of packing into of water with gained, stir on the limit, and the limit adds 1.5 parts of 25% ammoniacal liquor, and carries out 3 hours neutralization reactions at 70 ℃.Neutralization reaction is cooled to 40 ℃ with reactive system inside after finishing.Pack into then 43.8 parts in 18.7 parts of 40% acrylamides and water rise to after 65 ℃ the temperature in the reactive system, add 0.04 part of ammonium persulphate, and carry out reaction in 4 hours at 70 ℃～75 ℃.Its solids component 15% of the polymkeric substance of gained, viscosity 500cp(be with No. 3 rotors of BH type viscometer, change with 100 and measure, below identical).With this polymkeric substance as A liquid.
Secondly, replace beyond 18.7 parts of the acrylamides with 0.28 part of 18.0 parts of acrylamides and butyl acrylate, all the other carry out polymerization equally by the synthetic polymerization process of A liquid.The polymkeric substance that obtains, solids component are 15%, and viscosity is 450 cp.With this polymkeric substance as B liquid.
Production Example-2(is cationic)
Be in 93 parts of reactors of packing into of petroleum resin of 60 ℃ with softening temperature, heating and melting makes that temperature transfers to after 160 ℃ in the reactive system, adds 7.0 parts of maleic anhydrides, and carries out reaction in 6 hours at 200 ℃～210 ℃.Then, make that temperature is 170 ℃ in the system, add 8 parts of diethylin propylene diamines, carry out reaction in 3 hours at 200 ℃～210 ℃.After reaction finishes, make the temperature in the reactive system be adjusted to 150 ℃, add 10 parts of chloroethanols then, and under same temperature, carry out reaction in 4 hours.After reaction finishes, make the temperature in the reactive system be cooled to 120 ℃, under agitation slowly add 60 ℃ hot water, obtained solids component and be 40% water-soluble cationic resin.Resulting resin cation (R.C.) is as dispersing agent C.
Latexization
Embodiment-1
In pressurization emulsification still, pack into 24 parts of the maleation rosin (affixture of the toxilic acid of 88 parts of rosin and 12 parts) of 12 parts of glycerine esterification rosin (AV=11) and 12%, the heating consolute, temperature in the system is adjusted to after 150 ℃, under agitation, preprepared above-mentioned A liquid is warming up to 70 ℃ for 26.7 parts, and in the ramming system.Then, be pressed into 70 ℃ 37.3 parts of hot water.After being pressed into end, be cooled to 40 ℃ immediately, obtain solids component and be 40% latex sizing agent.
Embodiment-2
The petroleum resin of packing in pressurization emulsification still are (high gummy
#90 eastern nation chemical industry (strain) systems) 12 parts and 15% maleation rosin (affixtures of 85 parts of rosin and 15 parts of toxilic acids) are 24 parts, the heating consolute, and intrasystem temperature transferred to after 150 ℃, under agitation, in system, be pressed into 26.7 parts of above-mentioned A liquid that are adjusted to 70 ℃, and then be pressed into 70 ℃ 37.7 parts of hot water.After being pressed into end, be cooled to 40 ℃ immediately, obtained solids component and be 40% latex sizing agent.
Embodiment-3
The affixture that adds 37.2 parts of maleic anhydrides of interpolation 4% in rosiny glyceryl ester (AV=30), heating and melting, temperature in the system is adjusted to after 150 ℃, stirs and be pushed down into 3.2 parts of 25% polyoxyethylene distyryl phenol (15 moles of EO) sulphur sodium succinates.Be pressed into 13.3 parts of above-mentioned B liquid that are adjusted to 70 ℃ then, be pressed into 70 ℃ 46.3 parts of hot water again, and carry out being cooled to 40 ℃ immediately after emulsification disperses, obtain solids component and be 40% latex sizing agent.
Embodiment-4
In pressurization emulsification still, pack into 20 parts of the maleation rosin (affixtures of 88 parts of rosin and 12 parts of toxilic acids) of 12 parts of glycerine esterification rosin (AV=11) and 12%, heating and melting, and intrasystem temperature transferred to after 150 ℃, under agitation, 20 parts of preprepared above-mentioned dispersion agents (C) (8 parts of solids components) are warming up to 70 ℃, and in system, are pressed into.Be pressed into 70 ℃ 48 parts of hot water then, be pressed into end after, be cooled to 40 ℃ immediately, obtained solids component and be 40% latex.
Embodiment-5
In reactor, pack into 90 parts of rosin, heating and melting, and intrasystem temperature transferred to 180 ℃, add 10 parts of glycerine, the dehydration that slowly heats up, make intrasystem temperature be 250 ℃～280 ℃ and under this temperature 20 hours (the carboxylate AV=15 that obtains, 88 ℃ of softening temperatures (SP)) of reaction.Reaction was cooled to 150 ℃ to temperature in the system after finishing, and adds 5.0 parts of maleic anhydrides, 200 ℃～210 ℃ reactions 3 hours.Then, 31 parts of the resultant of reaction that obtain are packed in the pressurization emulsification stills, intrasystem temperature is adjusted to 150 ℃, and be pressed into the mixed solution of 20 parts of preprepared dispersion agents (C) and 1.0 parts of polyoxyethylene distyryl phenol.Be pressed into 70 ℃ 48 parts of hot water then, be pressed into end after, be cooled to 40 ℃ immediately, obtained solids component and be 40% latex.
Embodiment-6
Pointed out water emulsion that the foregoing description 1～5 is obtained in the present embodiment, the performance during as the neutralized paper sizing agent.Performance is that index is represented by the measured value of degree of sizing.As a comparative example, used the anionic latex sizing agent of the prior art that following method makes.
Pack in the reactor 900 parts of tolu rosin, heating and melting, and after temperature in the system is adjusted to 160 ℃～170 ℃, add 100 parts of fumaric acid, 200 ℃～210 ℃ reactions 3 hours.Then, in the 950 parts of pressurization emulsification stills of packing into of rosin with the rich horseization modification that obtains, and temperature in the system is adjusted into 150 ℃.After this, in pressurization emulsification still, be pressed into 200 parts of 25% preprepared 70 ℃ polyoxyethylene triphenylethylene phenol (EO=13) the sulphur sodium succinate aqueous solution.Then, be pressed into cooling immediately behind 70 ℃ 850 parts of the hot water, obtained solids component and be 50% latex sizing agent.
The performance comparison test
1) paper pulp: L/N(7/3) BKP
Beating degree: CSF=450 milliliter
Paper is heavy: 70g/m
2
The sizing agent add-on: with solids component calculating is that 0.3 weight %, 0.5 weight % and 0.7 weight %(are benchmark with paper pulp weight)
The Tai-Ace S 150 add-on: 1.0 weight %(are benchmark with paper pulp weight)
The cationic starch add-on: 0.5 weight %(is a benchmark with paper pulp weight)
Filler: light calcium carbonate 10 weight %(are benchmark with paper pulp weight)
Drying conditions: at 90 ℃, 2 minutes (use drum dryer)
Paper technology: paper pulp → Tai-Ace S 150 → cationic starch → applying glue → dilution → lime carbonate (pH 7.8)) → papermaking
Degree of sizing assay method: JIS P 8122(stockigt method)
(test-results)
Test portion sizing agent add-on 0.3 weight % 0.5 weight % 0.7 weight %
Embodiment-1 5 " 8 21 " 7 35 " 2
Embodiment-2 4 " 4 19 " 9 34 " 7
Embodiment-3 5 " 0 20 " 5 33 " 1
Embodiment-4 6 " 1 22 " 9 37 " 8
Embodiment-5 5 " 7 23 " 3 35 " 9
Comparative example 0 " 0 " 2 " 6
2) paper pulp: go up white waste paper and (contain CaCO
36%)
Beating degree: CSF=430 milliliter
Paper is heavy: 68 g/m
2
The sizing agent add-on: with solids component calculating is that 0.3 weight %, 0.5 weight % and 0.7 weight %(are benchmark with paper pulp weight)
The Tai-Ace S 150 add-on: 1.0 weight %(are benchmark with paper pulp weight)
Drying conditions: at 90 ℃, 2 minutes (use drum dryer)
Paper technology: paper pulp → Tai-Ace S 150 → applying glue → dilution (pH 7.5) → papermaking
Degree of sizing assay method: JIS P 8122(stockigt method)
(test-results)
Test portion sizing agent add-on 0.3 weight % 0.5 weight % 0.7 weight %
Embodiment-1 7 " 7 18 " 7 29 " 6
Embodiment-2 7 " 4 19 " 0 28 " 4
Embodiment-3 7 " 9 18 " 1 29 " 1
Embodiment-4 8 " 9 22 " 9 30 " 5
Embodiment-5 9 " 1 23 " 8 31 " 7
Comparative example 0 " 3 " 36 " 7
Can know that by The above results the water emulsion sizing agent of prepared in accordance with the method for the present invention has obviously good sizability.In contrast, commercially available anionic latex sizing agent does not show sizability or shows sizability hardly.
Claims (8)
1, a kind of sizing agent dispersion agent is the NH by styrene/acrylic or styrene/methacrylic acid mass polymer
4, K or Na salt and/or alkanolamine salt constitute with the water-soluble polymer of acrylamide or Methacrylamide graft polymerization.
2, a kind of preparation method of water emulsion sizing agent, this method is mixed 20～60 parts of weight of petroleum resin of petroleum resin or the unsaturated polyprotonic acid addition of α, β in 100 parts of weight of rosin of rosin or the unsaturated polyprotonic acid addition of α, β, and the mixture of gained used the described dispersion agent of claim 1 and disperses.
3, a kind of preparation method of water emulsion sizing agent, this method is in the rosin of rosin or the unsaturated polyprotonic acid addition of α, β, carry out esterification with polyvalent alcohol, to obtain acid number is 5～100 carboxylate, and with this carboxylate separately or the mixture of forming by 20～70 parts of weight of rosin of 100 parts of weight of this carboxylate and rosin or the unsaturated polyprotonic acid addition of α, β, the use described dispersion agent of claim 1 and disperseing.
4, a kind of preparation method of water emulsion sizing agent, this method is carried out esterification with rosin with polyvalent alcohol, and in the acid number that obtains is 5～50 carboxylate, add the unsaturated polyprotonic acid of α, β, then with the affixture that obtains, use the dispersion agent of claim 1 record to disperse.
5, the preparation method of each described water emulsion sizing agent in the claim 2～4 wherein in the described dispersion agent of claim 1, can and disperse with non-ionic type, aniorfic surfactant.
6, a kind of preparation method of water emulsion sizing agent, this method is with the rosin of rosin or the unsaturated polyprotonic acid addition of α, β, carry out esterification with polyvalent alcohol, to obtain acid number is 5～100 carboxylate, make this carboxylate separately or the mixture of forming by 20～70 parts of weight of rosin of 100 parts of weight of this carboxylate and rosin or the unsaturated polyprotonic acid addition of α, β then, use cationization petroleum resin, cationization rosin or cats product to be dispersion agent, and as required, add nonionic agent again and disperse.
7, a kind of preparation method of water emulsion sizing agent, this method is carried out esterification with rosin with polyvalent alcohol, and in the carboxylate of the acid number 5～50 that obtains, add the unsaturated polyprotonic acid of α, β and the affixture that obtains, with cationization petroleum resin, cationization rosin or cats product as dispersion agent, and as required, add nonionogenic tenside again and disperse.
8, the manufacture method of the described water emulsion sizing agent of each of claim 2～7 can re-use protective colloid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94103908 CN1109489A (en) | 1994-03-30 | 1994-03-30 | Method for preparation of disperser used in glue applying agent and aqueous emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94103908 CN1109489A (en) | 1994-03-30 | 1994-03-30 | Method for preparation of disperser used in glue applying agent and aqueous emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1109489A true CN1109489A (en) | 1995-10-04 |
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ID=5031330
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94103908 Pending CN1109489A (en) | 1994-03-30 | 1994-03-30 | Method for preparation of disperser used in glue applying agent and aqueous emulsion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063814C (en) * | 1997-12-03 | 2001-03-28 | 中国科学院广州化学研究所 | preparation of sizing synergist |
| CN1295014C (en) * | 2005-05-23 | 2007-01-17 | 山东轻工业学院 | Cationic dispersion rosin size |
| CN102995488A (en) * | 2012-12-05 | 2013-03-27 | 陕西科技大学 | Method for preparing cationic rosin/C9 petroleum resin sizing agent |
| CN103306162B (en) * | 2012-03-10 | 2017-09-19 | 荒川化学工业株式会社 | Rosin emulsion-type sizing agent, its manufacture method and paper |
| CN110205871A (en) * | 2019-06-24 | 2019-09-06 | 广州英科新材料有限公司 | A kind of rosin neutral sizing agent and preparation method thereof |
-
1994
- 1994-03-30 CN CN 94103908 patent/CN1109489A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063814C (en) * | 1997-12-03 | 2001-03-28 | 中国科学院广州化学研究所 | preparation of sizing synergist |
| CN1295014C (en) * | 2005-05-23 | 2007-01-17 | 山东轻工业学院 | Cationic dispersion rosin size |
| CN103306162B (en) * | 2012-03-10 | 2017-09-19 | 荒川化学工业株式会社 | Rosin emulsion-type sizing agent, its manufacture method and paper |
| CN102995488A (en) * | 2012-12-05 | 2013-03-27 | 陕西科技大学 | Method for preparing cationic rosin/C9 petroleum resin sizing agent |
| CN110205871A (en) * | 2019-06-24 | 2019-09-06 | 广州英科新材料有限公司 | A kind of rosin neutral sizing agent and preparation method thereof |
| CN110205871B (en) * | 2019-06-24 | 2022-04-12 | 广州英科新材料有限公司 | Neutral rosin sizing agent and preparation method thereof |
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