CN100510255C - Water resisting agent for coating of coated paper and preparation method thereof - Google Patents
Water resisting agent for coating of coated paper and preparation method thereof Download PDFInfo
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- CN100510255C CN100510255C CNB200510137118XA CN200510137118A CN100510255C CN 100510255 C CN100510255 C CN 100510255C CN B200510137118X A CNB200510137118X A CN B200510137118XA CN 200510137118 A CN200510137118 A CN 200510137118A CN 100510255 C CN100510255 C CN 100510255C
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Abstract
The invention provides water repellent agent used in coated paper coatings as chemical auxiliary agent and its manufacturing method. The coatings water repellent agent is water solution with 45%-55% working substance content composed by 40%-45% polyamide polyurea epichlorohydrin with -S-NH<SUB>2</SUB> radical and 5%-10% epoxy modification water solubility silicone oil. The manufacturing method includes the following steps: reacting diethylene tren and adipic acid at 120 centigrade degree for 1h; warming up and controlling the temperature at 165 centigrade degree for 1h; warming up to 190 centigrade degree for 2h; continually separating the product water in the reaction process; cooling to 110 centigrade degree and adding thiourea; reacting for 3h at 80 centigrade degree; adding epichlorohydrin and water; reacting for 40min at 70 centigrade degree; using 10% hydrochloric acid to neutralize to make the pH value reach 7.0; mixing with epoxy modification water solubility silicone oil. The invention overcomes the defect that the current water repellent agent has formaldehyde releasing pollution and working of paper is need curing after taking down from machine.
Description
Affiliated technical field
The present invention relates to painting processing paper and produce the water repellent agent of allocating in the used coating, and the preparation method of this water repellent agent.
Background technology
Employed water repellent agent in paper making and cloth coating coating generally all is an amino resins, is typically melamine resin the most.This class material uses as water repellent agent, can improve the moisture-resistant friction and the wet picking strength of coated paper, improves the printability of coated paper, reduces and falls hair, dry linting phenomenon.But this class water repellent agent product has a certain amount of formaldehyde and discharges in storage and use, and environment is polluted, and is detrimental to health.In addition, use paper that this class water repellent agent production comes out and cardboard behind machine down, need the regular hour to carry out slaking.This is because the thorough crosslinking curing of the adhesive in amino resins, especially melamine resin and the coating needs the long time, thereby makes paper and the cardboard produced be unfavorable for immediately in order to printing.This process has influenced production efficiency greatly.
Summary of the invention
Purpose of the present invention, providing does not a kind ofly have the water repellent agent that nuisance discharges, and this water repellent agent is after being used to produce, and the paper of following machine and cardboard need not carry out slaking.
Another object of the present invention provides the preparation method of this water repellent agent.
Water repellent agent provided by the present invention is characterized in that, has
The quality of the polyamide polyureas epoxychloropropane of group accounts for 40%-45%, and the quality of polyether modified water soluble silicone fluid accounts for 5%-10%, and all the other are water, and constituting solid content by them is 45%-55% the aqueous solution.
Water repellent agent with above-mentioned composition provided by the invention is prepared by following method:
Diethylenetriamine and adipic acid are reacted 1h at 120 ℃, heating up also, temperature control reacts 1h in 165 ℃, continue to heat up in 190 ℃ of reaction 2h, the water generation reaction part in the course of reaction in the continuous separation system is cooled to 110 ℃, in system, add thiocarbamide, in 80 ℃ of reaction 3h, add epoxychloropropane and water at last, at 70 ℃ of reaction 40min, with in 10% hydrochloric acid and the pH value to 7.0 of system, be cooled to 30 ℃ and had
The polyamide polyureas epoxychloropropane aqueous solution of group, more than the mol ratio of each material input be: diethylenetriamine: adipic acid: thiocarbamide: epoxychloropropane: water=1.2: 1.0: 1.6-2.0: 0.3-0.5: 25.0; In the polyamide polyureas epoxychloropropane aqueous solution of above preparation, add polyether modified water soluble silicone fluid, make the mass content of polyether modified water soluble silicone fluid in whole system, reach 5%-10%, and the solid content of the hierarchy of control is 45%-55%, stir, obtain water resisting agent for coating of coated paper.
The addition of thiocarbamide and epoxychloropropane can be regulated among the present invention, control the mean molecule quantity of polyamide polyureas epoxychloropropane with this, addition is the mean molecule quantity height greatly then, be embodied in the viscosity height of product, otherwise then mean molecule quantity is low, the viscosity of product also can be along with reduction, and product prepared in span of the present invention all can reach satisfied result of use.When addition is lower than span of the present invention, can makes the mean molecule quantity of product cross low and cause result of use poor; When addition during, can make that the mean molecule quantity of product is higher, thereby cause product generation gel and can not be used as water resisting agent for coating of coated paper greater than span of the present invention.
Water repellent agent provided by the present invention, in the polyamide polyureas epoxychloropropane wherein
Group and chlorethanol group can be effectively with coating in the hydroxyl crosslinking curing of adhesive.
Sulphur atom in the group has stronger electron donation, has higher activity, can form ionic bonding with adhesive (as carboxylic styrene butadiene latex, styrene-acrylic latex, soybean protein and starch etc.); The chloroethene alcohol radical then can form chemical covalent bond with adhesive; Active epoxy group in the polyether modified water soluble silicone fluid and the hydroxyl in the adhesive and carboxyl form ionic bond, and with fiber in the hydroxyl bonding, align thereby in coating, form, make hydrophobic grouping be oriented to coating surface, make full use of moisture-resistant friction and wet picking strength that organosilyl good hydrophobicity is given coating WATER RESISTANCE and Geng Gao.Its serviceability meets or exceeds traditional water repellent agents such as melamine resin, and particularly its printing adaptability is excellent more.
Polyamide polyureas epoxychloropropane and polyether modified water soluble silicone fluid in the water repellent agent of the present invention, when storing, condition is stable, does not have harmful substance to discharge; When the coating operation, along with finishing of drying process, they also will form the stable material of chemical property with adhesive and fiber crosslinking curing, and also can not cause them to decompose in dry run.
In the water repellent agent of the present invention, in the polyamide polyureas epoxychloropropane
With the chloroethene alcohol radical just can be effectively in the coating dry run with coating in the hydroxyl crosslinking curing of adhesive, and polyether modified water soluble silicone fluid has also been realized with the crosslinking curing of hydroxyl and carboxyl in this course and has been aligned, therefore, do not need to carry out slaking with this paper produced and cardboard, thereby improved production efficiency greatly.
Polyamide polyureas epoxychloropropane with preparation method's preparation of the present invention has
Group is than tradition having with urea production
The polyamide polyureas epoxychloropropane of group has stronger reactivity, and this is because sulphur atom has stronger electron donation, and is feasible faster with the present invention prepared water repellent agent and the adhesive crosslinking curing in the coating composition, in conjunction with more firm.And the present invention adopts polyether modified water soluble silicone fluid and polyamide polyureas epoxychloropropane to form synergy, has improved moisture-resistant friction, surface strength, gloss and the smoothness of paper and cardboard greatly, makes that the printability of paper and cardboard is stronger.
The specific embodiment
The invention will be further described by the following examples.
Embodiment one
Electronic stirring is equipped with in the adding of 1mol adipic acid, thermometer, in the four-necked bottle of condenser and water knockout drum, add diethylenetriamine 1.2mol, open and stir, be warming up to 120 ℃ of reaction 1h, temperature control is in 165 ℃ of reaction 1h, continue to be warming up to 190 ℃ of reaction 2h, condensed water is constantly got rid of, be cooled to 110 ℃, add the 1.6mol thiocarbamide, maintain the temperature at 80 ℃ of reaction 3h, add 0.5mol epoxychloropropane and 405ml water when reducing temperature to 70 ℃, maintain the temperature at 70 ℃ of reaction 40min, with 10% hydrochloric acid regulation system pH value to 7.0, obtain the polyamide polyureas epoxychloropropane aqueous solution, when temperature drops to 30 ℃, add the 90g polyether modified water soluble silicone fluid, stir 20min to evenly obtaining water resisting agent for coating of coated paper.
This coating water repellent agent is the light yellow transparency liquid of solid content 55%, and wherein polyamide polyureas epoxychloropropane accounts for 45%, and polyether modified water soluble silicone fluid accounts for 10%, and viscosity is 290mpas (25 ℃ in NDJ-79 type viscosimeter).
Embodiment two
Electronic stirring is equipped with in the adding of 1mol adipic acid, thermometer, in the four-necked bottle of condenser and water knockout drum, add diethylenetriamine 1.2mol, open and stir, be warming up to 120 ℃ of reaction 1h, temperature control is in 165 ℃ of reaction 1h, continue to be warming up to 190 ℃ of reaction 2h, condensed water is constantly got rid of, be cooled to 110 ℃, add the 1.8mol thiocarbamide, maintain the temperature at 80 ℃ of reaction 3h, add 0.4mol epoxychloropropane and 566.5ml water when reducing temperature to 70 ℃, maintain the temperature at 70 ℃ of reaction 40min, to 7.0, obtain the polyamide polyureas epoxychloropropane aqueous solution, with 10% hydrochloric acid regulation system pH value when temperature drops to 30 ℃, add the 51.5g polyether modified water soluble silicone fluid, stir 20min to evenly obtaining water resisting agent for coating of coated paper.
This coating water repellent agent is the light yellow transparency liquid of solid content 45%, and wherein polyamide polyureas epoxychloropropane accounts for 40%, and water-soluble silicon oil accounts for 5%, and viscosity is 360mpas (25 ℃ in NDJ-79 type viscosimeter).
Embodiment three
Electronic stirring is equipped with in the adding of 1mol adipic acid, thermometer, in the four-necked bottle of condenser and water knockout drum, add diethylenetriamine 1.2mol, open and stir, be warming up to 120 ℃ of reaction 1h, temperature control is in 165 ℃ of reaction 1h, continue to be warming up to 190 ℃ of reaction 2h, condensed water is constantly got rid of, be cooled to 110 ℃, add the 2.0mol thiocarbamide, maintain the temperature at 80 ℃ of reaction 3h, add 0.5mol epoxychloropropane and 541ml water when reducing temperature to 70 ℃, maintain the temperature at 70 ℃ of reaction 40min, with 10% hydrochloric acid regulation system pH value to 7.0, obtain the polyamide polyureas epoxychloropropane aqueous solution, when temperature drops to 30 ℃, add the 62.4g polyether modified water soluble silicone fluid, stir 20min to evenly obtaining water resisting agent for coating of coated paper.
This coating water repellent agent is the light yellow transparency liquid of solid content 48%, and wherein polyamide polyureas epoxychloropropane accounts for 42%, and polyether modified water soluble silicone fluid accounts for 6%, and viscosity is 480mpas (25 ℃ in NDJ-79 type viscosimeter).
Embodiment four
Electronic stirring is equipped with in the adding of 1mol adipic acid, thermometer, in the four-necked bottle of condenser and water knockout drum, add diethylenetriamine 1.2mol, open and stir, be warming up to 120 ℃ of reaction 1h, temperature control is in 165 ℃ of reaction 1h, continue to be warming up to 190 ℃ of reaction 2h, condensed water is constantly got rid of, be cooled to 110 ℃, add the 1.6mol thiocarbamide, maintain the temperature at 80 ℃ of reaction 3h, add 0.3mol epoxychloropropane and 432ml water when reducing temperature to 70 ℃, maintain the temperature at 70 ℃ of reaction 40min, with 10% hydrochloric acid regulation system pH value to 7.0, obtain the polyamide polyureas epoxychloropropane aqueous solution, when temperature drops to 30 ℃, add the 81g polyether modified water soluble silicone fluid, stir 20min to evenly obtaining water resisting agent for coating of coated paper.
This coating water repellent agent is the light yellow transparency liquid of solid content 52%, and wherein polyamide polyureas epoxychloropropane accounts for 43%, and polyether modified water soluble silicone fluid accounts for 9%, and viscosity is 120mpas (25 ℃ in NDJ-79 type viscosimeter).
Claims (3)
1, water resisting agent for coating of coated paper is characterized in that, has
The quality of the polyamide polyureas epoxychloropropane of group accounts for 40%-45%, and the quality of polyether modified water soluble silicone fluid accounts for 5%-10%, and all the other are water, and constituting solid content by them is 45%-55% the aqueous solution.
2, the method for preparation water resisting agent for coating of coated paper as claimed in claim 1: diethylenetriamine and adipic acid are reacted 1h at 120 ℃, heating up also, temperature control reacts 1h in 165 ℃, continue to heat up in 190 ℃ of reaction 2h, water generation reaction part in the course of reaction in the continuous separation system, be cooled to 110 ℃, in system, add thiocarbamide, in 80 ℃ of reaction 3h, add epoxychloropropane and water at last, at 70 ℃ of reaction 40min, with in 10% hydrochloric acid and the pH value to 7.0 of system, reduce the temperature to 30 ℃, had
The polyamide polyureas epoxychloropropane aqueous solution of group, more than the mol ratio of each material input be: diethylenetriamine: adipic acid: thiocarbamide: epoxychloropropane: water=1.2: 1.0: 1.6-2.0: 0.3-0.5: 25.0, in the polyamide polyureas epoxychloropropane aqueous solution of above preparation, add polyether modified water soluble silicone fluid, the mass content of epoxide modified silicone oil in whole system is 5%-10%, and the solid content of the hierarchy of control is 45%-55%, is stirred to evenly.
3, the preparation method of water resisting agent for coating of coated paper according to claim 2, preparation process is all under agitation carried out.
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| CNB200510137118XA CN100510255C (en) | 2005-12-30 | 2005-12-30 | Water resisting agent for coating of coated paper and preparation method thereof |
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| CNB200510137118XA CN100510255C (en) | 2005-12-30 | 2005-12-30 | Water resisting agent for coating of coated paper and preparation method thereof |
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| CN100510255C true CN100510255C (en) | 2009-07-08 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419158C (en) * | 2006-10-19 | 2008-09-17 | 上海东升新材料有限公司 | Coated waterproof agent, and preparation method |
| CN101403205B (en) * | 2008-11-13 | 2011-03-30 | 中南大学 | Coating water-repellent agent and preparation method thereof |
| CN101831070B (en) * | 2010-03-31 | 2011-11-16 | 上海东升新材料有限公司 | Modified coating water repellent agent and preparation method thereof |
| CN101831072B (en) * | 2010-03-31 | 2012-06-20 | 上海东升新材料有限公司 | Water-proofing agent for coated paper coatings and preparation method thereof |
| CN103524729B (en) * | 2013-10-17 | 2015-09-16 | 宁波环洋化工有限公司 | A kind of production method of mortar concrete admixture |
| CN104370859B (en) * | 2014-09-11 | 2016-08-24 | 浙江和新科技有限公司 | A kind of coating water repellent agent and its preparation method and application |
| CN104372714B (en) * | 2014-09-24 | 2016-10-05 | 九洲生物技术（苏州）有限公司 | A kind of papermaking coating reinforcing agent and its preparation method and application |
| CN105113327A (en) * | 2015-08-13 | 2015-12-02 | 合肥龙发包装有限公司 | Preparation method for AKD gel emulsifier |
| CN106750373A (en) * | 2016-11-24 | 2017-05-31 | 九洲生物技术（苏州）有限公司 | The preparation method of modified carboxyl styrene-butadiene latex dispersion liquid |
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2005
- 2005-12-30 CN CNB200510137118XA patent/CN100510255C/en active Active
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Owner name: HUBEI DAYA BIOLOGICAL TECHNOLOGY CO., LTD. Free format text: FORMER NAME: HUBEI DAYA CHEMICAL TECHN DEVELOPMENT CO., LTD. |
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Address after: 434000 No. 109, Beijing East Road, Hubei, Jingzhou Patentee after: HUBEI DAYA BIOLOGICAL TECHNOLOGY CO., LTD. Address before: 434000 No. 109, Beijing East Road, Hubei, Jingzhou Patentee before: Hubei Daya Chemical Techn Development Co., Ltd. |