CN104153249A - Paper surface sizing agent and preparation method thereof - Google Patents
Paper surface sizing agent and preparation method thereof Download PDFInfo
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- CN104153249A CN104153249A CN201410403840.2A CN201410403840A CN104153249A CN 104153249 A CN104153249 A CN 104153249A CN 201410403840 A CN201410403840 A CN 201410403840A CN 104153249 A CN104153249 A CN 104153249A
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Abstract
The invention provides a paper surface sizing agent. The sizing agent comprises 100 parts of molten alkyl ketene dimer, 25-100 parts of a cationic aqueous copolymer, 1-5 parts of a stabilizer and 270-610 parts of water, wherein the cationic aqueous copolymer and water form a cationic aqueous copolymer dispersion; and the cationic aqueous copolymer is obtained through a free radical polymerization reaction of an allyl cation monomer, a hydrophobic alkenyl monomer and a silane monomer. The invention also provides a preparation method of the paper surface sizing agent. The paper surface sizing agent can obviously improve the hydrophobicity of paper, reduce the Cobb value and improve the surface strength of the paper.
Description
Technical field
The present invention relates to a kind of paper technology, relate in particular to a kind of paper surface sizing agent and preparation method thereof.
Background technology
Papermaking is an ancient technology, can trace back to 105 years Christian eras, when paper is carried out to WATER REPELLENT TREATMENT but cannot know for sure.Approximately middle period the 17th century, just have and prevent the impregnated paper of ink and the writing paper of internal sizing.Animal glue is main at that time sizing agent, and aluminium alum is generally used as the curing agent of applying glue.The starch processing of early stage paper, just in order to make its lustrous surface.Within 1807, start to apply the applying glue of aluminium alum-rosin.To the 1950's, in succession there are various types of gum rosins, and the synthetic sizing agent such as AKD (alkyl ketene dimer) and ASA (alkenyl succinic anhydride).
Paper fibre, owing to containing a large amount of hydroxyls, can form hydrogen bond with water, so there is very strong hydrophilic tendency.Just can lose its most of intensity when page is immersed in water after saturated, this point is well suited for toilet paper, corrugating medium, but is unwanted to most of paper, as paper in the office, food boxes, minaudiere, grocery bag paper.Paper-making sizing is a kind of processing method in order to improve the impermeabilisation power of paper to water and liquid.
Paper-making sizing generally has two kinds of methods: one is top sizing, and paper web is after being shaped, being dried, and sizing agent can impose on paper surface by size press, coating machine or calender; Another kind is plasm-glue-blending, is sizing agent is added in paper making pulp, reaches the combination with paper web in paper forming process.The result of two kinds of processes can reduce the wet performance of paper to water, and top sizing also can reduce the hole of paper web.
Along with the development of neutral and alkali paper technology, as a kind of response type neutral and alkali synthetic sizing agent AKD and ASA etc., there is the features such as sizing efficiency is high, consumption is few, in papermaking, be widely used.Tradition sizing agent emulsion uses cationic starch as emulsifying agent and stabilizing agent, but the retention of this emulsion on fiber is lower, and slower with reacting of fiber, the applying glue curing time is long.
In recent years, along with the use of coated broke, deinked waste paper, high yield pulp, the raising of paper machine white water circulation closed degree and the use of other paper making additives, make the aggregate concentration of the interfering anionic impurity of wet end of machine more and more higher, increasing to the harm of wet end of machine operation.For better solving the problem that anionic impurity brings applying glue, especially improve the effect of sizing agent neutral and alkali applying glue, should adopt the polymer that charge density is higher to replace cationic starch to catch anionic impurity.
Chinese patent CN101173026A discloses a kind of cationic polymer emulsification sizing agent that adopts natural polymer glycerol polymerization and preparation method thereof, the slaking speed of the sizing agent emulsion applying glue obtaining, but surface strength of paper is increased little.
Summary of the invention
The present invention solves the aforementioned problems in the prior proposition, its objective is a kind of paper surface sizing agent that can improve paper hydrophobicity, reduction Cobb value and improve surface strength of paper is provided.
Another object of the present invention is to provide the preparation method of above-mentioned paper surface sizing agent.
For achieving the above object, the present invention is by the following technical solutions:
The invention provides a kind of paper surface sizing agent, it is characterized in that, this sizing agent comprises the parts by weight of following component and each component:
Wherein, described cation water-based copolymer and water form cation copolymer dispersion; Described cation water-based copolymer is by propenyl cationoid monomer, hydrophobicity alkenyl monomer and meets the silane monomer Raolical polymerizable of following general formula (I) and obtain;
Si(OR
1)
3[(R
2OCO)
nR
3C＝CH
2] (I)
R in formula
1, R
2for C
1-C
8alkyl, preferably C
1-C
3alkyl; R
3for hydrogen or C
1-C
8alkyl, preferably hydrogen or C
1-C
3alkyl; N is the integer of 0-4, preferably 0-1.
Preferably, described silane monomer is selected from one or more in vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, vinyltriethoxysilane.
Preferably, described stabilizing agent is zirconium oxychloride.
Preferably, the weight solid content of described sizing agent is 15%-25%, and the viscosity in the time of 25 DEG C is at 5-30mPas, and pH value is 2-4.
Preferably, described cation water-based copolymer comprises the parts by weight of following component and each component:
Wherein said silane monomer meets following general formula (I):
Si(OR
1)
3[(R
2OCO)
nR
3C＝CH
2] (I)
R in formula
1, R
2for C
1-C
8alkyl, preferably C
1-C
3alkyl; R
3for hydrogen or C
1-C
8alkyl, preferably hydrogen or C
1-C
3alkyl; N is the integer of 0-4, preferably 0-1.
Preferably, described propenyl cationoid monomer is selected from one or more in Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium salt, Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium salt, acrylic acid dimethylamino ethyl ester monochloro methane quaternary ammonium salt, acrylic acid dimethylamino ethyl ester benzyl chloride quaternary ammonium salt, diallyldimethylammonium chloride.
Preferably, described hydrophobicity alkenyl monomer is selected from one or more in styrene, methyl styrene, vinyltoluene, t-butyl styrene, dimethyl styrene, chlorovinyl toluene.
Preferably, described initator is selected from azo-initiator, organic peroxy class initator, preferably from 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4-methyl valeronitrile), 2, one or more in two (amidino groups propyl group) dihydrochlorides of 2 '-azo, dibenzoyl peroxide, hydrogen phosphide cumene, tertbutanol peroxide, cumyl peroxide, lauryl peroxide.
Preferably, described surfactant is selected from one or more in hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride.
Preferably, the weight solid content of described cation water-based copolymer is 20%-40%, and pH value is 2-6.
The present invention also provides a kind of preparation method of paper surface sizing agent, it is characterized in that, comprises the steps:
Step 1, prepare cation water-based copolymer according to described component and proportioning: in container, first add water and initator, be warming up to 60-95 DEG C, then in 1-3 hour, dropwise add propenyl cationoid monomer, hydrophobicity alkenyl monomer, silane monomer simultaneously, dropwise rear insulation 1-2 hour, finally add surfactant, be cooled to room temperature, obtain described cation water-based copolymer;
Step 2, prepare paper surface sizing agent according to described component and proportioning: in container, first add cation water-based copolymer and water, be warming up to 60-85 DEG C, add melting alkyl ketene dimer, homogeneous under 10-25MPa, be cooled to 40 DEG C and add below stabilizing agent, obtain described paper surface sizing agent.
The present invention also provides a kind of paper for surface sizing coating fluid, it is characterized in that, described paper surface sizing agent and starch, fluorescent whitening agent are calculated as the part by weight of 0.1-20:60-99.8:0.1-20 mixes by solid constituent, obtain paper for surface sizing coating fluid.
The present invention adopts the cation copolymer of high electric charge as the emulsifying agent of AKD wax, can obviously improve the effect of applying glue liquid, improves the surface strength of paper and reduces Cobb value.Possible reason is that the CATION in strong cation system can have ionic bond to be combined with the hydroxyl on paper fibre surface, carboxyl, thereby improves the surface strength of paper.In system, add a small amount of surfactant, can increase the stability of sizing agent emulsion, and can combine with the hydroxyl of paper fibre because surfactant has cation group, improve the hydrophobicity of paper.In system, add stabilizing agent zirconium oxychloride, can have some improvement to the stability of sizing agent emulsion.In sizing agent system, add the hydrophobic monomer component such as hydrophobicity alkenyl monomer, silane of a small amount of such as methyl (styrene), can improve significantly the surperficial hydrophobicity of paper.
The present invention adopts technique scheme, compared with prior art, there is following technique effect: a kind of paper surface sizing agent provided by the invention, the surface strength that can obviously improve hydrophobicity, reduction Cobb value and the raising paper of paper is a kind of sizing agent product that can meet high-performance for papermaking paint, environmental protection.
Detailed description of the invention
Below by specific embodiment, the present invention is carried out to detailed and concrete introduction, so that better understand the present invention, but following embodiment does not limit the scope of the invention.
embodiment 1
Synthesizing of cationic polymer:
A) 5 grams of styrene and 5 grams of vinyl silane triisopropoxides are mixed and made into mix monomer, for subsequent use.
B) 90 grams of Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium salts and 10 grams of deionized waters are mixed, dissolve completely, for subsequent use.
C) two 0.2 gram 2,2 '-azo (amidino groups propyl group) dihydrochlorides and 10 grams of deionized waters are mixed, dissolve completely, for subsequent use.
D) 133.5 grams of deionized waters are added to reactor, be warming up to 95 DEG C and add 2 in c) step, two (amidino groups propyl group) the dihydrochloride aqueous solution of 2 '-azo, then under 95 DEG C of conditions, drip a) step mix monomer and b) in cation mono liquid solution 1 hour.
E) 95 DEG C are incubated 1 hour.Insulation finishes to add 2g hexadecyltrimethylammonium chloride, is cooled to 25 DEG C, and 100 eye mesh screens filter.Obtain cationic polymer, weight solid content 39.5%, pH=5.95.
The preparation of surface sizing agent emulsion:
1) by 100gAKD wax 70 DEG C of meltings, for subsequent use;
2) 25g cationic polymer (embodiment 1 scheme makes), 608.3g deionized water are mixed, under agitation be warming up to 75 DEG C, improve mixing speed to 8000rpm/min, add the sizing agent wax liquid of melting under stirring, mixing time is 15 minutes.Under 75 DEG C, 25Mpa condition, homogeneous once.
3) be cooled to rapidly 25 DEG C, add 1g zirconium oxychloride, stir after 10 minutes and filter discharging with 100 eye mesh screens.The sizing agent emulsion of gained, weight solid content 15.03wt%, viscosity 11mPas (NDJ-1 rotary viscosity design determining), pH=3.96 (using PHS-3C Accurate pH instrumentation to obtain).
embodiment 2
Synthesizing of cationic polymer:
A) 10 grams of methyl styrenes and 10 grams of γ-methacryloxypropyl trimethoxy silane are mixed and made into mix monomer, for subsequent use.
B) 80 grams of Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium salts and 10 grams of deionized waters are mixed, dissolve completely, for subsequent use.
C) two 2 gram 2,2 '-azo (amidino groups propyl group) dihydrochlorides and 10 grams of deionized waters are mixed, dissolve completely, for subsequent use.
D) just 428 grams of deionized waters add reactor, be warming up to 95 DEG C and add 2 in c) step, two (amidino groups propyl group) the dihydrochloride aqueous solution of 2 '-azo, then under 95 DEG C of conditions, drip a) step mix monomer and b) in cation mono liquid solution 3 hours.
E) 60 DEG C are incubated 2 hours.Insulation finishes to add 10g octadecyl trimethyl ammonium chloride, is cooled to 25 DEG C, and 100 eye mesh screens filter.Obtain cationic polymer, weight solid content 20.1%, pH=2.28.
The preparation of surface sizing agent emulsion:
1) by 100gAKD wax 75 DEG C of meltings, for subsequent use;
2) 100g cationic polymer (embodiment 2 schemes make), 280g deionized water are mixed, be under agitation warming up to 65 DEG C, improve mixing speed to 10000rpm/min, add the sizing agent wax liquid of melting under stirring, mixing time is 5 minutes.Under 65 DEG C, 10Mpa condition, homogeneous once.
3) be cooled to rapidly 25 DEG C, add 5g zirconium oxychloride, stir 100 eye mesh screens after 10 minutes and filter discharging.The sizing agent emulsion of gained, weight solid content 24.93wt%, viscosity 30.1mPas (NDJ-1 rotary viscosity design determining), pH=2.05 (using PHS-3C Accurate pH instrumentation to obtain).
embodiment 3
Synthesizing of cationic polymer:
A) 7 grams of methyl styrenes and 8g vinyltriethoxysilane are mixed and made into mix monomer, for subsequent use.
B) by 85 grams of Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium salts, dissolve completely, for subsequent use.
C) two 1 gram 2,2 '-azo (amidino groups propyl group) dihydrochlorides and 10 grams of deionized waters are mixed, dissolve completely, for subsequent use.
D) 240.3 grams of deionized waters are added to reactor, be warming up to 85 DEG C and add 2 in c) step, two (amidino groups propyl group) the dihydrochloride aqueous solution of 2 '-azo, then under 85 DEG C of conditions, drip a) step mix monomer and b) in cation mono liquid solution 2 hours.
E) 85 DEG C are incubated 1.5 hours.Insulation finishes to add 4g octadecyl trimethyl ammonium chloride and 4g hexadecyltrimethylammonium chloride, is cooled to 25 DEG C, and 100 eye mesh screens filter.Obtain cationic polymer, weight solid content 30.1%, pH=4.03.
The preparation of surface sizing agent emulsion:
1) by 100gAKD wax 72 DEG C of meltings, for subsequent use;
2) 50g cationic polymer (embodiment 3 schemes make), 422g deionized water are mixed, be under agitation warming up to 70 DEG C, improve mixing speed to 9000rpm/min, add the sizing agent wax liquid of melting under stirring, mixing time is 10 minutes.Under 70 DEG C, 18Mpa condition, homogeneous once.
3) be cooled to rapidly 25 DEG C, add 3g zirconium oxychloride, stir 100 eye mesh screens after 10 minutes and filter discharging.The sizing agent emulsion of gained, weight solid content 20.10wt%, viscosity 13.8mPas (NDJ-1 rotary viscosity design determining), pH=2.95 (using PHS-3C Accurate pH instrumentation to obtain).
embodiment 4
Synthesizing of cationic polymer:
A) 6 grams of styrene and 4g vinyltriethoxysilane, 2g vinyl silane triisopropoxide are mixed and made into mix monomer, for subsequent use.
B) 88 grams of diallyldimethylammonium chlorides and 10 grams of deionized waters are mixed, dissolve completely, for subsequent use.
C) two 1.5 gram 2,2 '-azo (amidino groups propyl group) dihydrochlorides and 10 grams of deionized waters are mixed, dissolve completely, for subsequent use.
D) 176 grams of deionized waters are added to reactor, be warming up to 80 DEG C and add 2 in c) step, two (amidino groups propyl group) the dihydrochloride aqueous solution of 2 '-azo, then under 80 DEG C of conditions, drip a) step mix monomer and b) in cation mono liquid solution 2.5 hours.
E) 80 DEG C are incubated 1.2 hours.Insulation finishes to add 4g octadecyl trimethyl ammonium chloride, is cooled to 25 DEG C, and 100 eye mesh screens filter.Obtain cationic latex, weight solid content 34.2%, pH=3.41.
The preparation of surface sizing agent emulsion:
1) by 100gAKD wax 73 DEG C of meltings, for subsequent use;
2) 75g cationic polymer (embodiment 4 schemes make), 524.4g deionized water are mixed, under agitation be warming up to 72 DEG C, improve mixing speed to 8500rpm/min, add the sizing agent wax liquid of melting under stirring, mixing time is 12 minutes.Under 72 DEG C, 22Mpa condition, homogeneous once.
3) be cooled to rapidly 25 DEG C, add 2g zirconium oxychloride, stir 100 eye mesh screens after 10 minutes and filter discharging.The sizing agent emulsion of gained, weight solid content 18.01wt%, viscosity 11.75mPas (NDJ-1 rotary viscosity design determining), pH=3.24 (using PHS-3C Accurate pH instrumentation to obtain).
comparative example:
The sizing agent emulsion of preparing by the method for CN101173026A.
by embodiment 1-4 and comparative example, carry out application experiment by following technique
Experiment condition and process planning:
1, the preparation of surface size
Applying glue oxidized starch stirs and is warming up to 90-95 DEG C, after insulation gelatinization 30min, is adjusted to 65 DEG C of constant temperature, for subsequent use.
Gluing scheme: use above-mentioned oxidized starch solution and Cypres, starch concentration 10%.
Proportioning is: starch: Cypres: fluorescent whitening agent=50:1:4 (dry/dry/wet).
2, adopt 70g/m
2electro-photographic paper, as applying glue body paper, uses above-mentioned glue, on laboratory room small-sized sizing applicator, with identical resin added (one side 1.8g/m
2) carrying out respectively one side applying glue, the pattern after applying glue was dried on polisher with identical temperature, time (85 DEG C of * 20s), the Cobb value under detection pattern after machine and slaking 5min and the surface strength of pattern.
Wherein, Cobb value adopts testing standard GB/T 1540 " the absorptive determination method of paper and cardboard (suddenly methods) "; The surface strength of paper adopts testing standard GB/T 22365-2008 " mensuration of paper and cardboard printing surface strength ".
Criterion: the lower effect of Cobb value is better, and surface strength is the bigger the better.
Test data is as following table:
Can find out from above-mentioned application result: the surface sizing agent emulsion that uses embodiment of the present invention 1-4 to prepare, compared with comparative example, be applied to the top sizing in paper manufacture process, the Cobb value of gained paper is low, and surface strength is high, and effect is good.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the amendment done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (8)
1. a paper surface sizing agent, is characterized in that, this sizing agent comprises the parts by weight of following component and each component:
Wherein, described cation water-based copolymer and water form cation copolymer dispersion; Described cation water-based copolymer is by propenyl cationoid monomer, hydrophobicity alkenyl monomer and meets the silane monomer Raolical polymerizable of following general formula (I) and obtain;
Si(OR
1)
3[(R
2OCO)
nR
3C＝CH
2] (I)
R in formula
1, R
2for C
1-C
8alkyl, R
3for hydrogen or C
1-C
8alkyl, the integer that n is 0-4.
2. paper surface sizing agent according to claim 1, is characterized in that, described silane monomer is selected from one or more in vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, vinyltriethoxysilane.
3. paper surface sizing agent according to claim 1, is characterized in that, described stabilizing agent is zirconium oxychloride.
4. paper surface sizing agent according to claim 1, is characterized in that, the weight solid content of described sizing agent is 15%-25%, and the viscosity in the time of 25 DEG C is at 5-30mPas, and pH value is 2-4.
5. paper surface sizing agent according to claim 1, is characterized in that, described cation water-based copolymer comprises the parts by weight of following component and each component:
Wherein said silane monomer meets following general formula (I):
Si(OR
1)
3[(R
2OCO)
nR
3C＝CH
2] (I)
R in formula
1, R
2for C
1-C
8alkyl, R
3for hydrogen or C
1-C
8alkyl, the integer that n is 0-4;
Described propenyl cationoid monomer is selected from one or more in Dimethylaminoethyl Methacrylate monochloro methane quaternary ammonium salt, Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium salt, acrylic acid dimethylamino ethyl ester monochloro methane quaternary ammonium salt, acrylic acid dimethylamino ethyl ester benzyl chloride quaternary ammonium salt, diallyldimethylammonium chloride;
Described hydrophobicity alkenyl monomer is selected from one or more in styrene, methyl styrene, vinyltoluene, t-butyl styrene, dimethyl styrene, chlorovinyl toluene;
Described initator is selected from azo-initiator, organic peroxy class initator;
Described surfactant is selected from one or more in hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride.
6. paper surface sizing agent according to claim 5, is characterized in that, the weight solid content of described cation water-based copolymer is 20%-40%, and pH value is 2-6.
7. a preparation method for paper surface sizing agent, is characterized in that, comprises the steps:
Step 1, prepare cation water-based copolymer according to component claimed in claim 5 and proportioning: in container, first add water and initator, be warming up to 60-95 DEG C, then in 1-3 hour, dropwise add propenyl cationoid monomer, hydrophobicity alkenyl monomer, silane monomer simultaneously, dropwise rear insulation 1-2 hour, finally add surfactant, be cooled to room temperature, obtain described cation water-based copolymer;
Step 2, prepare paper surface sizing agent according to component claimed in claim 1 and proportioning: in container, first add cation water-based copolymer and water, be warming up to 60-85 DEG C, add melting alkyl ketene dimer, homogeneous under 10-25MPa, be cooled to 40 DEG C and add below stabilizing agent, obtain described paper surface sizing agent.
8. a paper for surface sizing coating fluid, it is characterized in that, paper surface sizing agent described in any one in claim 1-6 and starch, fluorescent whitening agent are calculated as the part by weight of 0.1-20:60-99.8:0.1-20 mixes by solid constituent, obtain paper for surface sizing coating fluid.
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| CN106368059A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Preparing method of surface sizing agent for corrugated paper, product and application of surface sizing agent |
| CN106368061A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | High-efficiency surface sizing agent and preparation method thereof |
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| CN106368061A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | High-efficiency surface sizing agent and preparation method thereof |
| CN114573767A (en) * | 2022-03-10 | 2022-06-03 | 北京马普新材料有限公司 | Copolymer, treating agent for paper, and paper product |
| CN114573767B (en) * | 2022-03-10 | 2023-02-28 | 北京马普新材料有限公司 | Copolymer, treating agent for paper, and paper product |
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Application publication date: 20141119 |