CN103122597A - Paper additive, stabilization method of paper additive and paper - Google Patents
Paper additive, stabilization method of paper additive and paper Download PDFInfo
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- CN103122597A CN103122597A CN2012101035780A CN201210103578A CN103122597A CN 103122597 A CN103122597 A CN 103122597A CN 2012101035780 A CN2012101035780 A CN 2012101035780A CN 201210103578 A CN201210103578 A CN 201210103578A CN 103122597 A CN103122597 A CN 103122597A
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Abstract
The present invention aims to provide a paper additive which can improve the viscosity stability. The paper additive comprises an amide compound obtained by reacting a monocarboxylic acid of 6 to 24 carbon atoms and/or a monocarboxylic acid derivaty of 6 to 24 carbon atoms and polyalkyl polyamine and an epihalohydrin reactant. The paper additive comprises a reactant (A) of the amide compound and epihalohydrin and a water-soluble electrolyte (B), and the amide compound is obtained by reacting the monocarboxylic acid of 6 to 24 carbon atoms and/or the monocarboxylic acid derivaty of 6 to 24 carbon atoms with the polyalkylene polyamine.
Description
Technical field
The present invention relates to paper additive, paper additive stabilization method and paper, more particularly relate to contain monocarboxylic acid and/or the monocarboxylic acid derivative of carbon number 6～24 and the resulting acid amides based compound of reaction and the reactant (A) of epoxyhalopropane and paper additive, paper additive stabilization method and the paper of water-soluble electrolyte (B) of poly-alkyl polyamine class of carbon number 6～24.
Background technology
Main component as the sizing agent of paper, the reactant of the resulting acid amides based compound of the reaction of carboxylic acid and/or carboxylic acid ester and poly-alkyl polyamine class and epoxyhalopropane (hereinafter referred to as " CAE resin ") is useful, belongs to known (being for example that Japanese examined patent publication 42-2922 communique and patent documentation 2 are Japanese examined patent publication 47-11306 communique referring to patent documentation).CAE resin purposes except making sizing agent, also can be made nontransparent degree reinforcing agent and porous reinforcing agent.Above-mentioned CAE resin belongs to known (being for example that Japanese JP 61-252400 communique and patent documentation 4 are Japanese Unexamined Patent 2000-273792 communique referring to patent documentation 3) as nontransparent degree reinforcing agent.And also belong to known (being for example Japanese JP 61-252400 communique referring to patent documentation 5) as the porous reinforcing agent.Yet, existing CAE resin, its viscosity stability still can not be of great satisfaction.
Summary of the invention
The object of the invention just is to provide a kind of paper that contains the reactant that the resulting acid amides based compound of reaction that makes specific monocarboxylic acid and/or specific monocarboxylic acid derivative and poly-alkyl polyamine class obtains with the epoxyhalopropane reaction again with additive, paper use additive stabilization method and paper, it can improve the viscosity stability that paper is used additive, and can also obviously reduce the foaming of copying when doing paper with additive in paper with regard to preferred mode.
The paper of the reactant that inventor etc. obtain with regard to containing the resulting acid amides based compound of reaction that makes specific monocarboxylic acid and/or specific monocarboxylic acid derivative and poly-alkyl polyamine class and reacting with epoxyhalopropane is again studied repeatedly with keen determination with the viscosity stability of additive, its result, discovery can improve viscosity stability by making water-soluble electrolyte be contained in paper with additive, and by using specific surfactant obviously to reduce to do to copy when paper uses with additive the foaming in paper, so reach the present invention.
That is, the object of the invention is achieved as follows:
＜1〉a kind of paper additive, is characterized in that, contains reactant (A) and the water-soluble electrolyte (B) of acid amides based compound and epoxyhalopropane; Above-mentioned acid amides based compound is to obtain by the monocarboxylic acid derivative of the monocarboxylic acid of carbon number 6～24 and/or carbon number 6～24 and the reaction of poly-alkyl polyamine class.
＜2〉by above-mentioned＜1〉described paper additive, wherein, water-soluble electrolyte (B) is that the salt of 1～13 acid consists of by the pKa of 25 ℃.
＜3〉by above-mentioned＜1〉or＜2〉described paper additive, wherein, water-soluble electrolyte (B) is carboxylate.
＜4〉by above-mentioned＜1 〉～＜3 in the described paper additive of any one, wherein, paper is with the water-soluble electrolyte (B) that contains 0.01～5 quality % in additive; Viscosity after preserving a week under 40 ℃, under 25 ℃ of solid contents 15%, temperature is in 2～50mPas scope.
＜5〉by above-mentioned＜1 〉～＜4 in the described paper additive of any one, wherein, also contain alkyl with carbon number 8～24 or the surfactant (C) of alkenyl.
＜6〉a kind of paper additive stabilization method, is characterized in that, the water-soluble electrolyte (B) that the salt that to allow the reactant (A) of acid amides based compound and epoxyhalopropane contain by the pKa of 25 ℃ be 1～13 acid consists of; Above-mentioned acid amides based compound is to obtain by the monocarboxylic acid derivative of the monocarboxylic acid of carbon number 6～24 and/or carbon number 6～24 and the reaction of poly-alkyl polyamine class.
＜7〉by above-mentioned＜6〉described paper additive stabilization method, wherein, also contain alkyl with carbon number 8～24 or the surfactant (C) of alkenyl.
＜8〉a kind of paper wherein, contains above-mentioned＜1 〉～＜5〉the middle described paper additive of any one.
Can provide a kind of and contain that the resulting acid amides based compound of reaction that makes specific monocarboxylic acid and/or specific monocarboxylic acid derivative and poly-alkyl polyamine class reacts with epoxyhalopropane again and the paper additive of the reactant that obtains, it can improve the viscosity stability that paper is used additive, and can also obviously reduce the foaming of copying when doing paper with additive in paper with regard to preferred mode.
The specific embodiment
The present invention is paper additive, paper additive stabilization method and paper, it is characterized in that, paper contains reactant (A) and the water-soluble electrolyte (B) of acid amides based compound and epoxyhalopropane with additive; Above-mentioned acid amides based compound is to obtain by the monocarboxylic acid derivative of the monocarboxylic acid of carbon number 6～24 and/or carbon number 6～24 and the reaction of poly-alkyl polyamine class.
As the monocarboxylic acid of carbon number 6～24 used in the present invention and the monocarboxylic acid derivative of carbon number 6～24, can exemplify out the ester etc. of the aliphatic acid of the acid anhydrides of aliphatic acid of aliphatic acid, carbon number 6～24 of carbon number 6～24 and carbon number 6～24.
As aliphatic acid can be following any: the straight chain fatty acid of carbon number 6～24, the aliphatic acid with side chain, saturated fatty acid and unrighted acid.In these aliphatic acid, especially preferred laurate, myristic acid, palmitic acid, stearic acid, behenic acid and oleic acid.These both can use separately a kind also can more than 2 kinds and use.
Can exemplify out the acid anhydrides of above-mentioned each aliphatic acid as the acid anhydrides of aliphatic acid.
Ester as aliphatic acid can exemplify out low-carbon-ester of above-mentioned each aliphatic acid etc.And as the low-carbon-ester of aliphatic acid, can exemplify out the methyl esters of aliphatic acid, the ethyl ester of aliphatic acid and the propyl ester of aliphatic acid etc.Fatty acid ester in the present invention can obtain by the esterification with alcohol of known aliphatic acid in the past.These both can use separately a kind also can more than 2 kinds and use.
In the present invention, can and use aliphatic dicarboxylic acid as the monocarboxylic acid beyond above-mentioned and/or the part of monocarboxylic acid derivative.Can exemplify out malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid etc. as aliphatic dicarboxylic acid.In addition, also can and use alkenyl succinic anhydrides and alkenyl ketene dimers (alkenyl ketene dymer).These both can use separately a kind also can more than 2 kinds and use.
as poly-alkyl polyamine class used in the present invention, can exemplify out ethylenediamine, diethylentriamine (Diethylenetriamine), trien (Triethylenetetramine), tetren (Tetraethylenpentamin), five ethene hexamines (Pentaethylenehexamine), six ethene seven amine (hexaethyleneheptamine), two propylene triamines (Dipropylenetriamine), three propylene tetramines (Tripropylenetetramine), hexamethylene diamine (hexamethylene diamine), the alkylene oxide of imino-bis-propylamine (iminobispropylamine) and these amines (alkylene oxide) additives, these both can use separately a kind also can more than 2 kinds and use.In the middle of these, preferred diethylentriamine, trien, tetren, especially more preferably tetren.These both can use separately a kind also can more than 2 kinds and use.
Although the reaction mol ratio of carboxylic acid and/or carboxylic acid ester and poly-alkyl polyamine class is not particularly limited, the amido of relatively poly-alkyl polyamine class, the reacting dose of monocarboxylic acid and/or monocarboxylic acid derivative is 0.3～0.99 equivalent, is preferably 0.4～0.8 equivalent.
The reaction of monocarboxylic acid and/or monocarboxylic acid derivative and poly-alkyl polyamine class is undertaken by being heated to 100～200 ℃.Reaction time is generally 0.5～10 hour, wherein preferred 2～6 hours.When reaction, the not restriction of method that carboxylic acid and/or carboxylic acid ester are mixed with poly-alkyl polyamine class usually preferably adds toward poly-alkyl polyamine class the method that carboxylic acid and/or carboxylic acid ester make reaction carry out smoothly gradually.Do not use the catalyst of amidation process can yet, if but use, also can use normally used catalyst in the amidation process such as the sulphonic acids such as sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid (p-toluenesulfonic acid) or phosphoric acid as the catalyst of amidation process.Its use amount, 1 mole of relatively poly-alkyl polyamine is generally 0.005～0.1 mole, preferred 0.01～0.05 mole.
For amide compound and the epoxyhalopropane that obtains paper additive of the present invention, make obtaining as described above reacts under 30～100 ℃.Can make the mixed solvent of water or water and organic solvent as reaction dissolvent.In order to make the resulting paper of the present invention emulsion stabilisation of additive, preferably make and contain surfactant, further, in order to reduce DCP (1,3-two chloro-2-propyl alcohol (1,3-dichloro-2-propanol)) etc. low molecule organic chloride, preferably carry out following 1 secondary response and 2 secondary responses.
The mixed solvent of water or water and organic solvent is made reaction dissolvent, and the mixture of amide compound and reaction dissolvent is remained in 30 ℃～69 ℃, adds epoxyhalopropane at this and makes and react.After adding epoxyhalopropane, further reaction temperature is remained in 30 ℃～69 ℃ and react.For sake of convenience, this reaction is called 1 secondary response.The time of 1 secondary response is preferably 5 minutes～and 3 hours.5 timesharing of reaction time less than, the effect that reduces the DCP content in the CAE resin is insufficient, and if 1 secondary response time surpassed 3 hours, the DCP content in resulting CAE resin does not very reduce, and merely only extends the reaction time and uneconomical.
After 1 secondary response has carried out reaction, heat up in 70 ℃～100 ℃, while keep this temperature to react.For sake of convenience, this reaction is called 2 secondary responses.As for the reaction time of 2 secondary responses, so long as get final product, be generally 1 hour～8 hours within the time that is enough to make reaction to finish.
As reaction dissolvent used in the present invention, can adopt the mixed solvent of water or water and organic solvent.Can exemplify out methyl alcohol, ethanol, isopropyl alcohol etc. as organic solvent, wherein preferred isopropyl alcohol.These both can use separately a kind to mix with water also can more than 2 kinds and use with water and mix.The use amount of water and organic solvent, blending ratio make amide compound dissolve equably necessary amount, mixing ratio when disperseing under reaction temperature as long as adopt.Usually, the reaction of amide compound and epoxyhalopropane is that the concentration at amide compound is 5～90%, the mixing ratio of water and organic solvent is to carry out under 100g: 0～100g.
In the reaction of amide compound and epoxyhalopropane, be 0.05～1.2 equivalent with respect to the molar weight of the epoxyhalopropane of the reactive hydrogen of the residual amine of acid amides based compound, be preferably 0.2～1.0 equivalent.If the molar weight of epoxyhalopropane is less than 0.05 equivalent, thereby the viscosity of CAE resin uprises and loses flowability, and can cause difficult treatment; And if surpass 1.2 equivalents, can cause again in the CAE resin DCP to contain quantitative change many.
At this, residual amine can be calculated by the amine value of measuring amino based compound.
Residual amine=amine value=(V * F * 0.5 * 56.1)/S
Wherein, the titer (cc) of the hydrochloric acid methanol liquid of V:1/2 regulation
The titer of the hydrochloric acid methanol liquid of F:1/2 regulation
S: the solid content (g) of the sample of taking
As epoxyhalopropane used in the present invention, can exemplify out chloropropylene oxide, epoxy bromopropane (Epibromohydrine) etc., wherein preferred chloropropylene oxide.
As surfactant used in the present invention, can use known surfactant in the past, for example can exemplify out non-ionic surface active agent, cationic surfactant, anionic surfactant, amphoteric surfactant etc.Wherein preferably use nonionic surfactant, cationic surfactant, especially cationic surfactant, improving being good at adhering to of paper pulp fiber, help to reduce in copying paper system and foam, therefore more preferably.Surfactant can add amide compound before reacting with epoxyhalopropane, perhaps the reaction of amide compound and epoxyhalopropane midway, the reaction of amide compound and epoxyhalopropane adds after finishing, paper preferably uses with 0.5～5% scope with using 0.1～10% in additive.If the content of surfactant greater than 10%, is difficult to reduce foaming when copying paper.
Can exemplify out as nonionic surfactant the compound (hereinafter referred to as Compound I) that represents with following general formula (1).These both can use separately also and can more than 2 kinds and use.
General formula (1)
R
11-A
11-(B
11O)
k-R
12
Yet (, in formula ,-A
11-expression-O-or COO-, R
11The alkyl of expression carbon number 5～23 or the alkenyl of carbon number 5～23, R
12Expression has acyl group or the hydrogen base of the alkenyl of the alkyl of alkenyl, carbon number 6～24 of the alkyl of carbon number 6～24 or carbon number 6～24 or carbon number 6～24, B
11O represents oxyethylene group and/or oxypropylene group, in the middle of oxyethylene group and oxypropylene group additional a kind or 2 kinds also can, k is 1～100, preferred 10～80.In addition, k is average additional molal quantity.)
The compound of above-mentioned general formula (1) expression for example can be by adding oxidative ethane and/or expoxy propane obtains in 1 mole, the aliphatic acid of the alcohol of carbon number 6～24 (preferred 10～22) or carbon number 6～24 (preferred 10～22), and, can also be by above-mentioned alkylene oxide (alkylene oxide) additives be carried out esterification with 1 mole, the aliphatic acid of carbon number 6～24 (preferred 10～22), perhaps, carry out etherificate and obtain with 1 mole of the alkyl halide of the alcohol of carbon number 6～24 (preferred 10～22) or carbon number 6～24 (preferred 10～22).The additional form of oxirane and/or expoxy propane both can be and also can be at random block, pressed 1 mole of add-on that adds 1～100 mole (preferred 10～80 moles) of aliphatic acid of alcohol or the carbon number 6～24 (preferred 10～22) of relative carbon number 6～24 (preferred 10～22).
As the alcohol of carbon number 6～24, can be straight chain alcohol, have any in alcohol, saturated alcohols and the unsaturated alcohol of side chain.The alcohol of preferred carbon number 10～22 in the middle of these alcohol, especially preferred laruyl alcohol, myristyl alcohol (myristyl alcohol), hexadecanol (cetyl alcohol), stearyl alcohol (stearyl alcohol), docosyl alcohol and oleyl alcohol.These both can use separately a kind also can more than 2 kinds and use.
As the aliphatic acid of carbon number 6～24, can be straight chain fatty acid, have any in aliphatic acid, saturated fatty acid and the unrighted acid of side chain.The aliphatic acid of preferred carbon number 10～22 in the middle of these aliphatic acid, especially preferred laurate, myristic acid, palmitic acid, stearic acid, behenic acid and oleic acid.These both can use separately a kind also can more than 2 kinds and use.
Can exemplify out the cationic surfactant of following general formula (2)～(4) expression.
General formula (2)
In general formula (2), R
21Alkyl or the alkenyl of expression carbon number 8～24, B
21O and B
22O represents oxyethylene group and/or oxypropylene group, in the middle of oxyethylene group and oxypropylene group additional a kind or 2 kinds also can, l and m on average add molal quantity, l and m sum are 1～70, preferred 10～60.
General formula (3)
In general formula (3), R
31And R
32Alkyl or the alkenyl of expression carbon number 8～24, B
31O represents oxyethylene group and/or oxypropylene group, in the middle of oxyethylene group and oxypropylene group additional a kind or 2 kinds also can, n on average adds molal quantity, is 1～70, preferred 10～60.
General formula (4)
In general formula (4), R
41Alkyl or the alkenyl of expression carbon number 8～24, Y represents the alkylidene of carbon number 2～6, B
41O, B
42O and B
43O represents oxyethylene group and/or oxypropylene group, in the middle of oxyethylene group and oxypropylene group additional a kind or 2 kinds also can, o～q on average adds molal quantity, o～q adds up to 1～70, preferred 10～60.
Consider from the viscosity stability this point of additive, paper of the present invention contains water-soluble electrolyte (B) with additive.Preferred water dissolubility electrolyte (B) adds in the reaction of amide compound and epoxyhalopropane midway or after the reaction end.With the densimeter that contains in additive, the content of water-soluble electrolyte (B) is 0.01～5 quality %, preferably in 0.05～2 quality % scope by paper.
In the present invention, water-soluble electrolyte (B) refers to the compound that ionizes in water.As suitable water-soluble electrolyte (B), the salt of acid of (preferred 1～13, more preferably 3～10) consists of to be-4～13 by the pKa of 25 ℃.PKa of the present invention is 25 ℃ of acid ionization constants in water, expression pKa n for the n salt of polyacid, specifically, if disodium citrate just represents the pKa2 of citric acid.Specifically, can exemplify out the neutralization generation salt of sour agent, alkaline agent and sour agent and alkaline agent.Wherein, above-mentioned sour agent can exemplify out the carboxylic acids such as formic acid, acetic acid, lactic acid, gluconic acid, butanedioic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, phthalic acid, acetic acid, benzoic acid, salicylic acid, gallic acid, diethyl barbituric acid; The amino acid such as amion acetic acid, alanine, valine, leucine, serine, glutamic acid, aspartic acid; The organic sulfonic acids such as ethyl sulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid, meta-xylene sulfonic acid (m-Xylene sulfonic acid); The sulfamic acids such as taurine; The inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, carbonic acid, silicic acid, aluminic acid etc.Above-mentioned alkaline agent can exemplify out the chain hydramine such as monoethanolamine, diethanol amine, triethanolamine; The inorganic alkali such as ammonia, NaOH, potassium hydroxide etc.Can exemplify out natrium citricum, Potassium Benzoate, ammonium chloride, sodium carbonate, dikalium phosphate, sulfuric acid monoethanolamine, No. 1 sodium metasilicate, No. 2 sodium metasilicate, No. 3 sodium metasilicate etc. with generation salt in above-mentioned sour agent and alkaline agent.This is wherein preferred coordinates the sour agent that is selected from carboxylic acid and/or the neutralization of its alkaline agent to generate salt.specifically, preferred sodium acetate (pKa=4.8), ammonium acetate (pKa=4.8), potassium acetate (pKa=4.8), natrium citricum (means sodium dihydrogen citrate (pKa1=3.1), disodium citrate (pKa2=4.8) and trisodium citrate (pKa3=6.4)), natrium malicum (meaning malic acid one sodium (pKa1=3.4) and malic acid disodium (pKa2=5.1)), sodium formate (pKa=3.8), adipic acid sodium (meaning adipic acid one sodium (pKa1=4.4) and adipic acid disodium (pKa2=5.4)).
The CAE resin can make its dispersion with known method in the past.When dispersion, add again after both can having added in advance above-mentioned water-soluble electrolyte (B) also can disperse.As known process for dispersing in the past, can be commutation emulsification, add surfactant or add surfactant after commutation emulsification again, also useful mechanical means dispersion.These independent uses might as well method also be used all out of question more than 2 kinds.As mechanical means, can exemplify out and spray the homodisperse methods of various known mulsers such as homogenizer, high cut-off type rotation emulsion dispersion machine, ultrasonic emulsification machine with mixer for well-distribution, high-voltage high-speed.
Be not particularly limited as containing the paper of paper of the present invention with additive, can exemplify out various paper and paperboard.the paper kind can exemplify out the PPC paper using, the ink-jet printer printing, the laser printer paper using, the form paper using, heat-transferring printing paper, the thermal sensitive recording body paper, the paper used for recording such as body paper are recorded in pressure-sensitive, print paper and its body paper, art paper, cast coated paper, the coating body paper such as high grade paint paper, brown paper, the package papers such as pure white coil paper, other also has writing folio, the books paper using, various printings, the various paper (Western paper) such as newpapers and periodicals paper using, the Manila cone, the blank sheet of paper basin, the paper container boards such as horsehit cone, lining, the paperboards such as plasterboard body paper.Can also exemplify out beyond paper improved wood, inorganic be construction material, such as sawdust-board (Particleboard), hardboard, softboard, rock cotton board etc.
When making paper of the present invention, usually, add of the present invention paper additive by relative paper pulp solid content as the usage ratio of 0.1～3 % by weight take solid content.Also have, paper of the present invention is distributed in the paper substrate body on the way with additive also available sizing agent sprayer, gate roll coater (gate roll coater), Shim adhesive applicator etc.
Paper of the present invention, can contain the bleaching such as kraft pulp or sulfite pulp or bleached chemical paper pulps not as paper pulp raw material, the bleaching such as ground wood pulp, mechanical pulp or thermo-mechanical pulp or do not bleach brilliant idea and stay the old paper paper pulp such as rate paper pulp, old newspaper, outdated magazine, old corrugated paper or the old paper of deinking.The mixture that also can contain in addition, the synthetic fiber such as above-mentioned paper pulp raw material and rock wool, asbestos or polyamide, polyimides, polyester, polyene and polyvinyl alcohol.
When making paper of the present invention, in order to embody the desired physical property of various paper kinds, also can use filler, sizing agent, the agent of dry paper power, moistening paper power reinforcing agent as required, additives such as staying reinforcing agent, drainability reinforcing agent.These both can use separately also and can more than 2 kinds and use.In addition, make an addition in paper stock after can also mixing with paper of the present invention these with additive in advance and use, be not particularly limited as for mixed method.
Can exemplify out clay, talcum powder and calcium carbonate etc. as filler, these both can use separately also and can more than 2 kinds and use.Can exemplify out as sizing agent: the aliphatic acid gel sizing agent as odium stearate; Rosin, fortified rosin, rosin ester are sizing agent; The water-based emulsion of alkenyl succinic anhydrides; The water-based emulsion of 2-oxetanes; The water-based emulsion of paraffin; The resulting cationic sizing agent of the reaction of carboxylic acid and polyamine; The water-based emulsion of the reactant of aliphatic alkyd and aliphatic amine or aliphatic alcohol and cationic polystyrene sizing agent etc.These both can use separately also and can more than 2 kinds and use.
Can exemplify out anionic property polyacrylamide, cationic polyacrylamide, amphiprotic polyacrylamide, cationic starch and amphoteric starch etc. as dry paper power reinforcing agent, these both can use separately also and can more than 2 kinds and use.And can exemplify out polyamide-epoxy chloropropane resin (Polyamide-epichlorohydrin resin), melamine resin and pollopas etc. as moistening paper power reinforcing agent, these both can use separately also and can and use with the anionic property polyacrylamide.
As stay reinforcing agent can exemplify out anionic property, cationic or both sexes high molecular weight polyacrylamide, Ludox and cationic starch and with and bentonite and cationic high molecular weight polyacrylamide and use etc.These both can use separately also and can more than 2 kinds and use.Can exemplify out polymine (Polyethyleneimine), cationic or both sexes or anionic property polyacrylamide etc. as the drainability reinforcing agent.These both can use separately also and can more than 2 kinds and use.
Also have, also can use as required the surperficial paper power such as coating starch, polyvinyl alcohol and acrylamide polymer reinforcing agent, dyestuff, coating, Cypres and the antilubricants etc. such as sizing agent sprayer, gate roll coater, Bill's knife type coater (Bill blade coater), calender (calendar).These both can use separately also and can more than 2 kinds and use.In addition can also use paper of the present invention with additive before, add aluminum sulfate afterwards or simultaneously.
Embodiment
Followingly illustrate the present invention according to embodiment and comparative example.But the present invention only is defined in these examples.In addition, in each example, unless special record is arranged, % refers to % by weight.
Production Example 1
Toward with dropping into diethylentriamine 10.3g (0.1 mole), tetren 170g (0.9 mole), 75% phosphoric acid 0.218g (0.005 mole) in 2 liters of four-hole round-bottomed flasks of thermometer, reflux condenser, mixer, dropping funel, after being warmed up to 130 ℃, add gradually tallow fatty acids { stearic acid/palmitic acid mixture (mixed weight is than 65/35) } 714g (2.3 moles).Be warmed up to 180 ℃, the water that generates discharged it is reacted 2 hour and obtain amide compound on one side.The acid value of resulting amide compound is 6, and the residual amine base unit weight is 2.3mmol/g.
Production Example 2
Toward with dropping into tetren 189g (1 mole), 75% phosphoric acid 0.218g (0.005 mole) in 2 liters of four-hole round-bottomed flasks of thermometer, reflux condenser, mixer, dropping funel, after being warmed up to 130 ℃, add gradually oleic acid 847g (3 moles).Be warmed up to 180 ℃, the water that generates discharged it is reacted 2 hour and obtain amide compound on one side.The acid value of resulting amide compound is 8, and the residual amine base unit weight is 1.9mmol/g.
Embodiment 1
Be added in the resulting product 100g of Production Example 1 (as 0.23 mole of amido) in 1 liter of four-hole round-bottomed flask with thermometer, reflux condenser, mixer, dropping funel, as poly(ethylene oxide) (40), cocounut oil alkyl ether 5g and the water 245g of surfactant (C), stirred 1 hour under 80 ℃.After being cooled to 60 ℃, add chloropropylene oxide 8.4g (0.091 mole) to stir 30 minutes.Then reactant liquor is placed in 80 ℃ and makes reaction after 1 hour, on one side cooling reactant liquor add 10% aqueous sodium acetate solution 45.2g as water-soluble electrolyte (B) on one side, add water solid content adjusted to 15%.This intactly is used as the paper additive.
Table 1 provided make shortly past after viscosity and 40 ℃ under viscosity, foaminess, leavening effect after preserving 7.
Embodiment 2～17, comparative example 1～2
Kind and consumption such as the table 1 of acid amides based compound (A), water-soluble electrolyte (B), surfactant (C) are all the same with embodiment 1 with the exception of this.Table 1 provided make shortly past after viscosity and 40 ℃ under viscosity, leavening effect, foaminess after preserving 7.
＜leavening effect, foaminess 〉
Adopt the square handshcet former to carry out papermaking test to embodiment 1～17 and resulting each paper of comparative example 1～2 with additive.By visual to the foamed state of copying the resulting plain boiled water of paper carried out judging (* ... many, △ foams ... foaming is few, zero ... foaming is few), also resulting paper has been measured density (according to Japanese JISP8118 standard).
＜copy paper slip spare 〉
Use paper pulp: bleached kraft pulp (coniferous tree/broad leaf tree=1/9) concentration 2.4%
Beating degree (CSF) 410
The adding rate of medicine and order of addition:
Adding rate all refers to the solid content of relative paper pulp
Calcium carbonate (TP121 processed of Okutama Kogyo Co., Ltd.) 10% → cationic starch, 0.5% → embodiment 1～17, resulting certain paper of comparative example 1～2 are with additive 1% → copy paper with the square handshcet former
Copy paper grammes per square metre: 80g/m
2
Drying condition: 100 ℃ * 100sec (use cylindrical drier)
Table 1
must point out, the pKa of 25 ℃ about the water-soluble electrolyte (B) in table 1, malic acid one sodium is 3.4 (pKa1), calcium chloride is-3.7 (pKa), the sulfuric acid disodium is 2.0 (pKa2), sodium chloride is-3.7 (pKa), sodium bicarbonate is 6.4 (pKa1), sodium hydrogen phosphate is 2.2 (pKa1), sodium acetate is 4.8 (pKa), ammonium acetate is 4.8 (pKa), potassium acetate is 4.8 (pKa), disodium citrate is 4.8 (pKa2), sodium formate is 3.8 (pKa), adipic acid one sodium is 4.4 (pKa1).
When only adding paper using additive when adding medicine, the density of handmade paper is 0.69g/cm
2
Cocounut oil alkyl in table 1 is the alkyl of carbon number 6～18 or the mixture of alkenyl, mainly contains lauryl.Also has the average additional molal quantity of the numeral oxyethylene group in the surfactant title unquote in table 1.(B) content in table 1 represents the paper concentration of water-soluble electrolyte (B) contained in additive.
From result shown in table 1 obviously as can be known, paper of the present invention is being brought into play excellent effect with additive aspect the low-density of paper, simultaneously, even if do not have significant viscosity to raise after 1 week under 40 ℃ yet, restriction with aspects such as can reducing significantly keeping and transportation, and, used the embodiment 2～9 of compound (C) and embodiment 11～17 to make to copy that in paper, foaminess obviously reduces, so very useful in actual use.
Claims (8)
1. a paper additive, is characterized in that, contains reactant (A) and the water-soluble electrolyte (B) of acid amides based compound and epoxyhalopropane; Above-mentioned acid amides based compound is to obtain by the monocarboxylic acid derivative of the monocarboxylic acid of carbon number 6～24 and/or carbon number 6～24 and the reaction of poly-alkyl polyamine class.
2. by paper additive claimed in claim 1, it is characterized in that, water-soluble electrolyte (B) is that the salt of 1～13 acid consists of by the pKa of 25 ℃.
3. by the described paper additive of claim 1 or 2, it is characterized in that, water-soluble electrolyte (B) is carboxylate.
4. by the described paper additive of any one in claim 1～3, it is characterized in that, paper is with the water-soluble electrolyte (B) that contains 0.01～5 quality % in additive; Viscosity after preserving a week under 40 ℃, under 25 ℃ of solid contents 15%, temperature is in 2～50mPas scope.
5. by the described paper additive of any one in claim 1～4, it is characterized in that, also contain alkyl with carbon number 8～24 or the surfactant (C) of alkenyl.
6. a paper additive stabilization method, is characterized in that, the water-soluble electrolyte (B) that the salt that to allow the reactant (A) of acid amides based compound and epoxyhalopropane contain by the pKa of 25 ℃ be 1～13 acid consists of; Above-mentioned acid amides based compound is to obtain by the monocarboxylic acid derivative of the monocarboxylic acid of carbon number 6～24 and/or carbon number 6～24 and the reaction of poly-alkyl polyamine class.
7. by paper claimed in claim 6 additive stabilization method, it is characterized in that, also contain alkyl with carbon number 8～24 or the surfactant (C) of alkenyl.
8. a paper, is characterized in that, contains the described paper additive of any one in claim 1～5.
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| JP2011253336A JP5891735B2 (en) | 2011-11-18 | 2011-11-18 | Paper additive, method for stabilizing paper additive, and paper |
| JP2011-253336 | 2011-11-18 |
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| CN (1) | CN103122597B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104011293A (en) * | 2012-12-03 | 2014-08-27 | 星光Pmc株式会社 | Method For Manufacturing Paperboard |
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| JP6701536B2 (en) * | 2017-01-31 | 2020-05-27 | 星光Pmc株式会社 | PAPER ADDITIVE, PROCESS FOR PRODUCING THE SAME, AND PAPER CONTAINING PAPER ADDITIVE |
| CN113022185B (en) * | 2021-01-29 | 2023-03-28 | 广东冠豪高新技术股份有限公司 | Production process of water-based digital ink-jet transfer printing intermediate medium |
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| JP2003147692A (en) * | 2001-11-06 | 2003-05-21 | Japan Pmc Corp | Additive for paper and paper including the same |
| JP2007031898A (en) * | 2005-07-28 | 2007-02-08 | Seiko Pmc Corp | Method for producing paper additive, the resultant paper additive and paper |
| CN101765630A (en) * | 2007-07-30 | 2010-06-30 | 佐治亚-太平洋化工品有限公司 | Method of stabilizing aqueous cationic polymers |
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| DE3515479A1 (en) * | 1985-04-30 | 1986-10-30 | Bayer Ag, 5090 Leverkusen | Process for making paper or paper-like materials |
| JP4506290B2 (en) * | 2004-06-02 | 2010-07-21 | 星光Ｐｍｃ株式会社 | Paper additive, paper and method for producing the same |
| JP2008025074A (en) * | 2006-07-20 | 2008-02-07 | Akira Okada | Water dispersant for hydrophobizing agent and method for producing the same |
| JP2009149732A (en) * | 2007-12-19 | 2009-07-09 | Kao Corp | Method for producing polyamideamine-epihalohydrin resin |
| JP5347480B2 (en) * | 2008-12-17 | 2013-11-20 | 星光Ｐｍｃ株式会社 | Softener for paper |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147692A (en) * | 2001-11-06 | 2003-05-21 | Japan Pmc Corp | Additive for paper and paper including the same |
| JP2007031898A (en) * | 2005-07-28 | 2007-02-08 | Seiko Pmc Corp | Method for producing paper additive, the resultant paper additive and paper |
| CN101765630A (en) * | 2007-07-30 | 2010-06-30 | 佐治亚-太平洋化工品有限公司 | Method of stabilizing aqueous cationic polymers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104011293A (en) * | 2012-12-03 | 2014-08-27 | 星光Pmc株式会社 | Method For Manufacturing Paperboard |
| CN104011293B (en) * | 2012-12-03 | 2016-02-17 | 星光Pmc株式会社 | Paperboard manufacture method |
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| Publication number | Publication date |
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| JP2013108189A (en) | 2013-06-06 |
| JP5891735B2 (en) | 2016-03-23 |
| CN103122597B (en) | 2015-06-24 |
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