CN1793505A - Water-retaining agent for coating of coated paper and preparation method thereof - Google Patents
Water-retaining agent for coating of coated paper and preparation method thereof Download PDFInfo
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Abstract
The invention provides coated paper coatings molding moisture agent and its manufacturing method. The molding moisture agent is the composite of carboxymethyl se cellulose sodium and carboxymethyl sulfo ethyl starch sodium and polyvinyl pyrrolidon. Its manufacturing method includes the following steps: using 28% hydrogen peroxide to process purified cotton or wood pulp cake or corn starch or potato starch with more than 90% alpha-cellulose content in 90% alcohol above 40 centigrade degree; orderly adding chloroacetic acid, chloroethene sodium sulfonate, and sodium hydroxide; controlling the reaction temperature at 55 centigrade degree for 6h to gain carboxymethyl se cellulose sodium and carboxymethyl sulfo ethyl starch sodium; neutralizing resultant pH value at 7.0; separating solids; washing by 80% alcohol and drying to gain produce; mixing the produce and polyvinyl pyrrolidon in proportion to gain coated paper coating molding moisture agent. The invention can ensure higher molding moisture value to make the storage and moving viscosity of the coated coatings more stable.
Description
Affiliated technical field
The present invention relates to employed water-retaining agent for coating in the painting processing paper production, and the preparation method of this water retention agent.
Background technology
Water-retaining agent for coating is one of chemical assistant of preparation coating composition, and its quality can relate to the strength of coating of coated paper.The raising of strength of coating will rely on the adhesive of being allocated on the one hand, just needs the auxiliary of outstanding water-retaining agent for coating on the other hand.The use of outstanding water-retaining agent for coating can make adhesive evenly distribute in coating, and can be to bodystock paper and coating surface migration; When the water retention value of water-retaining agent for coating is hanged down, will cause the water retention value of coating on the low side, described two kinds of migrations just have generation in various degree; If these two kinds migrations take place, will make adhesive skewness in coating, the service efficiency of adhesive also can decrease, thereby influences the intensity of coating.In addition, the quality of water-retaining agent for coating also can relate to the viscosity stability of the coating composition of being prepared.Coating composition is a suspension system, and outstanding water retention agent should be able to make coating have stable storage viscosity, and has stable operation viscosity when coating, so just can help the normal stable operation of coating machine.
Traditional water-retaining agent for coating of coated paper mainly contains casein, polyvinyl alcohol, sodium carboxymethylcellulose.Casein makes institute's coatings formulated store the non-constant of viscosity stability, and easily makes coating putrid and deteriorated, is eliminated; The use of polyvinyl alcohol can cause the operation viscosity of coating very unstable, and the solid content of coating can only reach 30 ~ 40%, and the drying load of paper machine is big, can not adapt to the requirement of high-speed coating, can only be used for the airblade coating of low speed; Sodium Tvlose is the performance generally used a until now water-retaining agent for coating relatively preferably, can be used for high-speed blade coating and other high-speed coating mode, but the coating composition water retention value with its preparation is still desirable not to the utmost, make strength of coating be subjected to certain influence, in addition, this water retention agent makes the storage of institute's coatings formulated and operation viscosity understable, increases in time and viscosity uprises, this differs the coating thickness of each batching batch paper product that front and back produce, and influences the steady quality of paper product.Though can solve because of dope viscosity changes the problem that causes the coating layer thickness variation by regulating measures such as scraper aborning, regulate pretty troublesome, wayward.
Summary of the invention
Purpose of the present invention, provide a kind of water retention value that makes coating in the coated paper coatings, the storage viscosity of coating and water-retaining agent for coating that the operation viscosity stability more is better than Sodium Tvlose of being formulated into, with the strength of coating of raising coated paper and the uniformity of coating layer thickness.
Another object of the present invention provide a kind of preparation method of this water-retaining agent for coating, and preparation method's prepared coating water retention agent has different range of viscosities thus, to adapt to the needs of different paper kinds and different coating machine production processes.
Water-retaining agent for coating provided by the present invention is the compound of one kind of multiple compositions, and it is made of with respective quality percentage following material:
The carboxymethyl sulfoethyl cellulose is received and carboxymethyl sulfoethyl Starch Sodium accounts for 70%～90%, and polyvinylpyrrolidone accounts for 30%～10%; Carboxymethyl sulfoethyl cellulose sodium and carboxymethyl sulfoethyl Starch Sodium respectively account for 50% in the two.
Water-retaining agent for coating of coated paper with above-mentioned composition provided by the present invention, method preparation that can be following:
With alpha-cellulose content greater than 90% purified cotton or wood pulps and cornstarch or potato starch, in 90% ethanol in 40 ℃ with hydrogen peroxide treatment 5～30min of 28%, drop into monoxone, chloroethene sodium sulfonate, NaOH successively, control reaction temperature is at 55 ℃ of reaction 6h, obtain carboxymethyl sulfoethyl cellulose sodium and carboxymethyl sulfoethyl Starch Sodium, with in acetic acid or the hydrochloric acid and product pH value to 7.0, separate solid content, wash and dry products therefrom, above-mentioned product and polyvinylpyrrolidone are mixed with 80% ethanol;
The ingredient proportion of used material is:
The mol ratio of purified cotton or wood pulps and cornstarch or potato starch is 1: 1
The ingredient proportion of the mass number of the volume number of reaction medium 90% ethanol and purified cotton or wood pulps and cornstarch or potato starch is: 5: 1, unit was: ml/g or Kg/L
The mol ratio of monoxone, chloroethene sodium sulfonate, NaOH and purified cotton or wood pulps and cornstarch or potato starch is: 1: 0.02: 2.4: 1
The quality that feeds intake of hydrogen peroxide is 5% of purified cotton or wood pulps and cornstarch or a potato starch quality
The mass ratio of carboxymethyl sulfoethyl cellulose sodium and carboxymethyl sulfoethyl Starch Sodium and polyvinylpyrrolidone is 7～9: 3～1.
Water-retaining agent for coating provided by the present invention, be on the basis of traditional water retention agent sodium carboxymethylcellulose, to introduce the sulfoethyl group, increased salt tolerance, helped the enhancing of water retention, and the variation that coating operation viscosity is increased in time gradually has the inhibition effect; The carboxymethyl sulfoethyl Starch Sodium that is had not only has good water-retaining property, but also has the excellent shear desaturation, can help the paint flow sex change to strengthen; The polyvinylpyrrolidone that is had has the good dispersiveness to coating, film forming and water retention property, the good dispersiveness of coating is helped improving the stability of coating.The shear thinning effect of the water-retaining property of carboxymethyl sulfoethyl cellulose sodium excellence, appropriate carboxymethyl sulfoethyl Starch Sodium and the peptizaiton of polyvinylpyrrolidone, the storage and the operation stability of coating composition had both been helped to improve, make it have good flowability again, the comprehensive synergy of each component, can improve the water retention value of coating and the storage and the operation viscosity of stable coating when making water-retaining agent for coating of the present invention in allocating coating composition into effectively.
Preparation method provided by the present invention, owing to adopted the chloroethene sodium sulfonate as reaction mass, in sodium carboxymethylcellulose and sodium carboxymethyl starch, introduced the sulfoethyl group, overcome the problem of they viscosity stability differences, thereby also improved the storage of coating and the stability of operation viscosity, simultaneously, because composite polyvinylpyrrolidone, utilize its dispersiveness and excellent water-retaining property good, make that coating composition is stable more and water-retaining property is better coating; By regulating the processing time of described hydrogen peroxide to material, can obtain the coating water retention agent of different viscosities scope, to adapt in different paper kinds and the different coating machine production process different requirements to dope viscosity, when processing time during at 25-30min, the viscosity of water-retaining agent for coating is in 5～10mpas (25 ℃ in Brookfield viscosimeter) scope, when processing time during at 20-25min, the viscosity of water-retaining agent for coating is in 10～30mpas scope, when processing time during at 15-20min, the viscosity of water-retaining agent for coating is in 30～100mpas scope, when processing time during at 5-15min, the viscosity of water-retaining agent for coating is in 100～300mpas scope.
The specific embodiment
The present invention will be described by the following examples.
Embodiment one:
2kmol refinement purified cotton that contains 92% alpha-cellulose and 2kmol cornstarch put in the 5000L reactor that has stirring, inject the ethanol of 3240L content 90%, be warming up to 40 ℃, the hydrogen peroxide 32.4kg of adding 28%, handle 30min, drop into 4kmol monoxone, 0.02kmol chloroethene sodium sulfonate, 9.6kmol NaOH successively, temperature control is in 55 ℃ of reaction 6h, with the neutralize pH value of product of acetic acid is 7.0, separates solid content, with 80% ethanol washing dry gained target product also.
Get above product 700Kg and drop in the double cone mixer, add polyvinylpyrrolidone 300Kg, puddle, obtain the 1000Kg water-retaining agent for coating to evenly.
Get above finished product 2.00g (over dry) and be dissolved in the 98ml deionized water, recording viscosity in 25 ℃ with the Brookfield viscosimeter is 6mpas.
Prepare typical coating composition and do contrast test, gained data such as following table with the water retention agent sodium carboxymethylcellulose of external import identical viscosities:
| Coating water retention value (s) | Dope viscosity (mpas) | Leave standstill dope viscosity (mpas) behind the 24h | Dope viscosity (mpas) behind the operation 2h | Dope viscosity (mpas) behind the operation 8h | Coated paper strength of coating (m/s) | The coated paper coating uniformity | ||||
| Water retention agent of the present invention | 36 | 1100 | 1130 | Rate of change | 1150 | Rate of change | 1180 | Rate of change | 1.98 | +++ |
| 2.73％ | 4.55％ | 7.27％ | ||||||||
| The import carboxymethyl cellulose | 31 | 1280 | 1330 | Rate of change | 1390 | Rate of change | 1460 | Rate of change | 1.93 | ++ |
| 3.91％ | 8.59％ | 14.06％ | ||||||||
Annotate: the coating water retention value detects with AA-GWR250 coating water retention value analyzer, and dope viscosity detects with the Brookfield viscosimeter, and strength of coating detects with IGT picking strength instrument, and the coating uniformity is many more excellent more with "+".
Embodiment two:
2kmol refinement purified cotton that contains 92% alpha-cellulose and 2kmol potato starch put in the 5000L reactor that has stirring, inject the ethanol of 3240L content 90%, be warming up to 40 ℃, the hydrogen peroxide 32.4kg of adding 28%, handle 22min, drop into 4kmol monoxone, 0.02kmol chloroethene sodium sulfonate, 9.6kmol NaOH successively, temperature control is in 55 ℃ of reaction 6h, with the neutralize pH value of product of acetic acid is 7.0, separates solid content, with 80% ethanol washing dry gained target product also.
Get above product 780Kg and drop in the double cone mixer, add polyvinylpyrrolidone 220Kg, puddle, obtain the 1000Kg water-retaining agent for coating to evenly.
Get above finished product 2.00g (over dry) and be dissolved in the 98ml deionized water, recording viscosity in 25 ℃ with the Brookfield viscosimeter is 12mpas.
Prepare typical coating composition and do contrast test, gained data such as following table with the water retention agent sodium carboxymethylcellulose of external import identical viscosities:
| Coating water retention value (s) | Dope viscosity (mpas) | Dope viscosity (mpas) behind the static 24h | Dope viscosity (mpas) behind the operation 2h | Dope viscosity (mpas) behind the operation 8h | Coated paper strength of coating (m/s) | The coated paper coating uniformity | ||||
| Water retention agent of the present invention | 43 | 1180 | 1210 | Rate of change | 1195 | Rate of change | 1230 | Rate of change | 2.25 | +++ |
| 2.54％ | 1.27％ | 4.24％ | ||||||||
| The import carboxymethyl cellulose | 38 | 1390 | 1450 | Rate of change | 1490 | Rate of change | 1580 | Rate of change | 2.17 | ++ |
| 4.32％ | 7.19％ | 13.67％ | ||||||||
Annotate: the coating water retention value detects with AA-GWR250 coating water retention value analyzer, and dope viscosity detects with the Brookfield viscosimeter, and strength of coating detects with IGT picking strength instrument, and the coating uniformity is many more excellent more with "+".
Embodiment three:
2kmol refinement wood pulps that contains 92% alpha-cellulose and 2kmol potato starch put in the 5000L reactor that has stirring, inject the ethanol of 3240L content 90%, be warming up to 40 ℃, the hydrogen peroxide 32.4kg of adding 28%, handle 16min, drop into 4kmol monoxone, 0.02kmol chloroethene sodium sulfonate, 9.6kmol NaOH successively, temperature control is in 55 ℃ of reaction 6h, with the neutralize pH value of product of hydrochloric acid is 7.0, separates solid content, with 80% ethanol washing dry gained target product also.
Get above product 840Kg and drop in the double cone mixer, add polyvinylpyrrolidone 160Kg, puddle, obtain the 1000Kg water-retaining agent for coating to evenly.
Get above finished product 2.00g (over dry) and be dissolved in the 98ml deionized water, recording viscosity in 25 ℃ with the Brookfield viscosimeter is 58mpas.
Prepare typical coating composition and do contrast test, gained data such as following table with the water retention agent sodium carboxymethylcellulose of external import identical viscosities:
| Coating water retention value (s) | Dope viscosity (mpas) | Leave standstill dope viscosity (mpas) behind the 1h | Dope viscosity (mpas) behind the operation 2h | Dope viscosity (mpas) behind the operation 8h | Coated paper strength of coating (m/s) | The coated paper coating uniformity | ||||
| Water retention agent of the present invention | 48 | 1300 | 1310 | Rate of change | 1320 | Rate of change | 1380 | Rate of change | 2.05 | +++ |
| 0.77％ | 1.54％ | 6.15％ | ||||||||
| The import carboxymethyl cellulose | 42 | 1980 | 2000 | Rate of change | 2040 | Rate of change | 2100 | Rate of change | 2.03 | ++ |
| 1.01％ | 3.03％ | 6.06％ | ||||||||
Annotate: the coating water retention value detects with AA-GWR250 coating water retention value analyzer, and dope viscosity detects with the Brookfield viscosimeter, and strength of coating detects with IGT picking strength instrument, and the coating uniformity is many more excellent more with "+".
Embodiment four:
2kmol refinement wood pulps that contains 92% alpha-cellulose and 2kmol cornstarch put in the 5000L reactor that has stirring, inject the ethanol of 3240L content 90%, be warming up to 40 ℃, the hydrogen peroxide 32.4kg of adding 28%, handle 10min, drop into 4kmol monoxone, 0.02kmol chloroethene sodium sulfonate, 9.6kmol NaOH successively, temperature control is in 55 ℃ of reaction 6h, with the neutralize pH value of product of hydrochloric acid is 7.0, separates solid content, with 80% ethanol washing dry gained target product also.
Get above product 900Kg and drop in the double cone mixer, add polyvinylpyrrolidone 100Kg, puddle, obtain the 1000Kg water-retaining agent for coating to evenly.
Get above finished product 2.00g (over dry) and be dissolved in the 98ml deionized water, recording viscosity in 25 ℃ with the Brookfield viscosimeter is 180mpas.
Prepare typical coating composition and do contrast test, gained data such as following table with the water retention agent sodium carboxymethylcellulose of external import identical viscosities:
| Coating water retention value (s) | Dope viscosity (mpas) | Leave standstill dope viscosity (mpas) behind the 24h | Dope viscosity (mpas) behind the operation 2h | Dope viscosity (mpas) behind the operation 8h | Coated paper strength of coating (m/s) | The coated paper coating uniformity | ||||
| Water retention agent of the present invention | 51 | 1450 | 1465 | Rate of change | 1460 | Rate of change | 1500 | Rate of change | 2.13 | +++ |
| 1.03％ | 0.69％ | 3.45％ | ||||||||
| The import carboxymethyl cellulose | 48 | 2060 | 2095 | Rate of change | 2095 | Rate of change | 2140 | Rate of change | 2.07 | ++ |
| 1.70％ | 1.70％ | 3.88％ | ||||||||
Annotate: the coating water retention value detects with AA-GWR250 coating water retention value analyzer, and dope viscosity detects with the Brookfield viscosimeter, and strength of coating detects with IGT picking strength instrument, and the coating uniformity is many more excellent more with "+".
Claims (3)
1, a kind of water-retaining agent for coating of coated paper is characterized in that, is made of with the respective quality ratio following material:
Carboxymethyl sulfoethyl cellulose sodium and carboxymethyl sulfoethyl Starch Sodium account for 70%～90%, and polyvinyl pyrrolidone accounts for 30% ~ 10%; Carboxymethyl sulfoethyl fiber sodium and carboxymethyl sulfoethyl Starch Sodium respectively account for 50% in the two.
2, a kind of preparation method of water-retaining agent for coating of coated paper as claimed in claim 1, it is characterized in that alpha-cellulose content greater than 90% purified cotton or wood pulps and cornstarch or potato starch, in 90% ethanol in 40 ℃ with hydrogen peroxide treatment 5 ~ 30min of 28%, drop into monoxone successively, the chloroethene sodium sulfonate, NaOH, control reaction temperature is at 55 ℃ of reaction 6h, obtain carboxymethyl sulfoethyl fiber sodium and carboxymethyl sulfoethyl Starch Sodium, with in acetic acid or the hydrochloric acid and product pH value to 7.0, separate solid content, with washing of 80% ethanol and dry products therefrom, products therefrom and polyvinylpyrrolidone are mixed;
The ingredient proportion of used material is:
The mol ratio of purified cotton or wood pulps and cornstarch or potato starch is 1: 1
The ingredient proportion of the mass number of the volume number of reaction medium 90% ethanol and purified cotton or wood pulps and cornstarch or potato starch is: 5: 1, unit was: ml/g or Kg/L
The mol ratio of monoxone, chloroethene sodium sulfonate, NaOH and purified cotton or wood pulps and cornstarch or potato starch is: 1: 0.02: 2.4: 1
The quality that feeds intake of hydrogen peroxide is 5% of purified cotton or wood pulps and cornstarch or a potato starch quality
The mass ratio of carboxymethyl sulfoethyl cellulose sodium and carboxymethyl sulfoethyl Starch Sodium and polyvinylpyrrolidone is 7～9: 3～1.
3. a kind of method for preparing water-retaining agent for coating of coated paper according to claim 2, when the range of viscosities of the prepared coating composition water retention agent of needs was respectively 5～10mpas, 10～30mpas, 30～100mpas, 100～300mpas, the processing time of hydrogen peroxide was respectively 25～30min, 20～25min, 15～20min, 5～15min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965053A (en) * | 2012-12-10 | 2013-03-13 | 甘肃圣邦新材料有限公司 | Method for preparing sulfoethyl-carboxymethyl-crosslinked starch based wallpaper adhesive |
| CN108101999A (en) * | 2016-11-25 | 2018-06-01 | 中石化石油工程技术服务有限公司 | A kind of sulfoalkylation starch, its preparation method and application |
| CN112210020A (en) * | 2020-09-28 | 2021-01-12 | 河南省化工研究所有限责任公司 | Preparation method and application of cold water instant high amylose starch |
| CN114232382A (en) * | 2021-11-16 | 2022-03-25 | 苏州美盈森环保科技有限公司 | Printable water-retaining coating, preparation method and application |
| CN116042191A (en) * | 2022-11-10 | 2023-05-02 | 四川康荣石油化工科技有限公司 | Composite plugging material and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3742106A1 (en) * | 1987-12-11 | 1989-06-22 | Wolff Walsrode Ag | CARBOXYMETHYLSULFOETHYL CELLULOSE AND PROCESS FOR THE PRODUCTION THEREOF |
| US5079348A (en) * | 1989-05-24 | 1992-01-07 | Merck & Co., Inc. | Film-forming size composition |
| CN1064081A (en) * | 1992-01-31 | 1992-09-02 | 中国科学院上海有机化学研究所 | The manufacturing novel method of sodium starch glycolate |
| DE4241286A1 (en) * | 1992-12-08 | 1994-06-09 | Wolff Walsrode Ag | Highly substituted carboxymethyl sulfoethyl cellulose ethers, process for their preparation and use in textile printing color pastes |
| DE4241289A1 (en) * | 1992-12-08 | 1994-06-09 | Wolff Walsrode Ag | Highly substituted carboxymethyl sulfoethyl cellulose ether (CMSEC), process for its production and use in textile printing |
| CN1075149A (en) * | 1993-02-09 | 1993-08-11 | 罗纲 | The new synthetic process of sodium starch glycolate |
| CN1046293C (en) * | 1994-09-09 | 1999-11-10 | 扬中县江岛精细化工厂 | Modified corn starch dyeing paste and its preparation |
| DE19842962A1 (en) * | 1998-09-19 | 2000-03-23 | Wolff Walsrode Ag | Aqueous formulation for surface preparation and coating of paper and cardboard contained sulfoethylcellulose ether as cobinder |
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2005
- 2005-12-30 CN CNB2005101371175A patent/CN100365209C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965053A (en) * | 2012-12-10 | 2013-03-13 | 甘肃圣邦新材料有限公司 | Method for preparing sulfoethyl-carboxymethyl-crosslinked starch based wallpaper adhesive |
| CN102965053B (en) * | 2012-12-10 | 2015-08-26 | 甘肃圣邦布兰卡新材料有限公司 | The preparation method of sulfoethyl-carboxymethyl-cross-linking starch base Wall paper adhesive |
| CN108101999A (en) * | 2016-11-25 | 2018-06-01 | 中石化石油工程技术服务有限公司 | A kind of sulfoalkylation starch, its preparation method and application |
| CN112210020A (en) * | 2020-09-28 | 2021-01-12 | 河南省化工研究所有限责任公司 | Preparation method and application of cold water instant high amylose starch |
| CN112210020B (en) * | 2020-09-28 | 2022-02-22 | 河南省化工研究所有限责任公司 | Preparation method and application of cold water instant high amylose starch |
| CN114232382A (en) * | 2021-11-16 | 2022-03-25 | 苏州美盈森环保科技有限公司 | Printable water-retaining coating, preparation method and application |
| CN116042191A (en) * | 2022-11-10 | 2023-05-02 | 四川康荣石油化工科技有限公司 | Composite plugging material and application thereof |
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| CN100365209C (en) | 2008-01-30 |
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