CN103937434B - A kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent - Google Patents
A kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent Download PDFInfo
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- CN103937434B CN103937434B CN201410170674.6A CN201410170674A CN103937434B CN 103937434 B CN103937434 B CN 103937434B CN 201410170674 A CN201410170674 A CN 201410170674A CN 103937434 B CN103937434 B CN 103937434B
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Abstract
The invention discloses a kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent, in paper reuse, affect in order to solve existing double gummed paper sizing agent the problem that paper quality even affects paper shaping.The preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent of the present invention, adopts and introduce sulfo group on the monomer of alkyd polycondensation, significantly increase the wetting ability of polycondensation product.The present invention is compared with sizing agent conventional in prior art, its cohesive strength is improved obviously, and in paper reuse process, dissolving significantly reduces with colloidalmaterial (DCS) and cationic charge demand, and waste paper is easy to size degradation, reuse difficulty and cost reduce greatly, and wet end of machine efficiency is significantly improved.
Description
Technical field
The present invention relates to adhesive bookbinding sizing agent technical field, particularly a kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent.
Background technology
Double gummed paper books unsewn binding hot melt adhesive is one of domestic-developed hot melt adhesive kind the earliest, and it is high that principal feature books turn over planeness when opening; Weather resistance is strong, deflects 4000 times and still keeps intensity; Spine planeness is high, and Amount of spread is few, cold-resistant, heat-resisting, once solidification can not be softened, can use in wide temperature range.Be basic raw material with polyether glycol, be aided with multiple additives and polyisocyanic acid polyisocyanate polyaddition, obtain reaction type polyurethane hot-melt adhesive.Such as, but due to the restriction (particularly accounting for primary and secondary students' textbook of integral part) being subject to books price, make the quality of this field glue there is many problems, bonding strength is low, low temperature embrittlement, and the life-span is short, and product is based on low and middle-grade.Current domestic double gummed paper books unsewn binding hot melt adhesive is EVA type, polyurethanes hot melt adhesive is used for the unsewn binding of double gummed paper books in a large number abroad.
The patent of invention that Authorization Notice No. is " CN1021811259B " discloses a kind of adhesive bookbinding polyurethane hot melt and preparation method thereof, belongs to urethane preparing technical field.Polyester polyol and additive are placed in reactor and heat by the present invention, stir lower vacuum hydro-extraction, then lower the temperature; Get hexamethylene diisocyanate and diphenylmethanediisocyanate
It is the important measures of China's papermaking Realizing Forestry Sustainable Development that waste paper is recycled, and energy-conservation, lower consumption, subtract dirt, synergy is remarkable.The use of hot melt adhesive produces material impact to double gummed paper printed matter recycling characteristic, hot melt adhesive is combined with paper closely on the one hand, be difficult in paper Treatment for Reuse process be separated, cause the hot melt adhesive in remaining paper pulp to form the paper defects such as spot, transparency, affect sense organ and the quality of recycled writing paper; On the other hand, hot melt adhesive, for having hydrophobic nature, is difficult to dispersion, produces adhesive in reuse process in water, and the hot melt adhesive be dispersed in water, for reducing wet end of machine cationic auxiliary usefulness, affects paper and is shaped, reduce fiber bonding properties.Therefore, high-hydrophilic hot melt adhesive is developed significant for the efficiency utilization of double gummed paper printed matter.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent, in paper reuse, affect in order to solve existing double gummed paper sizing agent the problem that paper quality even affects paper shaping.
For solving the problem, the technical solution used in the present invention is:
A preparation method for double gummed paper wetting ability adhesive bookbinding sizing agent, comprises the following steps:
1) according to weight parts, by 50 ~ 150 parts of succinic acid and 1 ~ 5 part of octadecanoic acid mixing, stir, pass into rare gas element, be warming up to 188 ~ 194 DEG C, keep mechanical stirring;
2) drip 50 ~ 60 weight part 1-methylol-2-hydroxy-ethane potassium sulfonates, after dropwising, be warming up to 196 ~ 206 DEG C;
3) 1 ~ 3 weight part polycondensation catalyst is added;
4) drip 120 ~ 180 weight part pentanediols, after dropwising, be warming up to 208 ~ 216 DEG C, continue reaction 15 ~ 20min;
5) be cooled to 188 ~ 194 DEG C, add 1 ~ 3 weight part paraffin, 3 ~ 15 parts by weight binder, 2 ~ 6 parts by weight of filler, 0.1 ~ 1 weight part antioxidant, mix and stir, cooling.
Wherein, rare gas element plays a protective role, and can be nitrogen or helium; Octadecanoic acid is as additional an acidic catalyst; Polycondensation catalyst can be tetrabutyl titanate, potassium fluotitanate and antimony glycol; 1-methylol-2-hydroxy-ethane potassium sulfonate for introducing strongly hydrophilic group sulfo group in polycondensation product.
Preferably, described polycondensation catalyst is antimony glycol.
Preferably, evenly drip described 1-methylol-2-hydroxy-ethane potassium sulfonate, and dropwise in 20 ~ 25min.Evenly slowly drip, 1-methylol-2-hydroxy-ethane potassium sulfonate in reaction system is evenly distributed, contributes to follow-up reaction even.
Preferably, evenly drip described pentanediol, and dropwise in 30 ~ 45min.Evenly slowly drip pentanediol, the yield of polycondensation product can be increased to a certain extent.
Preferably, described binding agent comprises 2 ~ 10 weight part carboxy nitrile rubbers, 1 ~ 5 weight part water-based tackifying resin.The use of aqueous tackifier resin, further increases the wetting ability of the double gummed paper adhesive bookbinding sizing agent that the inventive method obtains.
Preferably, described weighting agent is talcum powder.Weighting agent can be at least one in talcum powder, titanium dioxide, calcium carbonate, is preferably talcum powder.
Preferably, described antioxidant is Tenox PG.
Preferably, described rare gas element is nitrogen.Nitrogen cost is low, can not cause atmospheric pollution.
Beneficial effect of the present invention is:
The present invention is compared with sizing agent conventional in prior art, its cohesive strength is improved obviously, and significantly reduce with colloidalmaterial (DCS) and cationic charge demand owing to dissolving containing more hydrophilic radical (sulfonic group) paper reuse process in sizing agent, waste paper is easy to size degradation, reuse difficulty and cost reduce greatly, and wet end of machine efficiency is significantly improved.The books and periodicals using this sizing agent to bind are in paper reuse process, and sizing agent is water-soluble, and paper reuse does not affect paper quality, also do not affect paper and are shaped.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
Add succinic acid and 2 grams of octadecanoic acids of quality 100 grams, pass into nitrogen, mixed by mechanical stirring, be warmed up to 188 DEG C, keep mechanical stirring, 60 grams of 1-methylol-2-hydroxy-ethane potassium sulfonates are evenly dripped at 22min, then 198 DEG C are warmed up to, add 1.5 grams of antimony glycols, evenly 150 grams of pentanediols are dripped in 40min, be warmed up to 208 DEG C after pentanediol drips and continue reaction 20min, reduce the temperature to 194 DEG C, add 5 grams of carboxy nitrile rubbers, 3 grams of aqueous tackifier resins, 2 grams of paraffin, 4 grams of talcum powder, 0.5 gram of Tenox PG, mix and blend 10min cools, encapsulation.
The sizing agent cohesive strength 5.62MPa of preparation, melting viscosity 3.15Pas, softening temperature 87.1 DEG C, temperature limit of brittleness-3.2 DEG C, hardness 82.7; Normal temperature aqueous solubilities 99.1% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 0.042%, cationic charge demand 1.75 μ eq/g; Elongation at break 395%, recovery of elasticity number of times 12000 times.
Embodiment 2
Add succinic acid and 2 grams of octadecanoic acids of quality 100 grams, pass into nitrogen, mixed by mechanical stirring, be warmed up to 194 DEG C, keep mechanical stirring, evenly 50 grams of 1-methylol-2-hydroxy-ethane potassium sulfonates are dripped in 25min, then 200 DEG C are warmed up to, add 1.5 grams of antimony glycols, evenly 140 grams of pentanediols are dripped in 40min, be warmed up to 208 DEG C after pentanediol drips and continue reaction 15min, reduce the temperature to 194 DEG C, add 7 grams of carboxy nitrile rubbers, 4 grams of aqueous tackifier resins, 1 gram of paraffin, 3 grams of talcum powder, 0.8 gram of Tenox PG, mix and blend 10min cools, encapsulation.
The sizing agent cohesive strength 5.54MPa of preparation, melting viscosity 3.42Pas, softening temperature 89.5 DEG C, temperature limit of brittleness-3.8 DEG C, hardness 86.1 normal temperature aqueous solubilities 99.0% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 0.036%, cationic charge demand 1.65 μ eq/g; Elongation at break 420%, recovery of elasticity number of times 13500 times.
Embodiment 3
Add succinic acid and 2 grams of octadecanoic acids of quality 80 grams, pass into nitrogen, mixed by mechanical stirring, be warmed up to 190 DEG C, keep mechanical stirring, evenly 55 grams of 1-methylol-2-hydroxy-ethane potassium sulfonates are dripped in 20min, then 201 DEG C are warmed up to, add 1.5 grams of antimony glycols, 125 grams of pentanediols are evenly dripped at 40min, be warmed up to 208 DEG C after pentanediol drips and continue reaction 18min, reduce the temperature to 194 DEG C, add 8 grams of carboxy nitrile rubbers, 4 grams of aqueous tackifier resins, 3 grams of paraffin, 6 grams of talcum powder, 0.8 gram of Tenox PG, mix and blend 10min cools, encapsulation.
The sizing agent cohesive strength 5.39MPa of preparation, melting viscosity 4.16Pas, softening temperature 91.3 DEG C, temperature limit of brittleness-4.2 DEG C, hardness 84.6; Normal temperature aqueous solubilities 99.2% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 0.046%, cationic charge demand 1.54 μ eq/g; Elongation at break 415%, recovery of elasticity number of times 13700 times.
Embodiment 4
Add succinic acid and 4 grams of octadecanoic acids of quality 130 grams, pass into nitrogen, mixed by mechanical stirring, be warmed up to 194 DEG C, keep mechanical stirring, 55 grams of 1-methylol-2-hydroxy-ethane potassium sulfonates are evenly dripped at 20min, then 200 DEG C are warmed up to, add 1.5 grams of antimony glycols, 175 grams of pentanediols are evenly dripped at 40min, be warmed up to 208 DEG C after pentanediol drips and continue reaction 18min, reduce the temperature to 190 DEG C, add 4 grams of carboxy nitrile rubbers, 5 grams of aqueous tackifier resins, 2 grams of paraffin, 4 grams of talcum powder, 1 gram of Tenox PG, mix and blend 10min cools, encapsulation.
The sizing agent cohesive strength 5.53MPa of preparation, melting viscosity 4.56Pas, softening temperature 88.7 DEG C, temperature limit of brittleness-4.0 DEG C, hardness 83.2; Normal temperature aqueous solubilities 99.4% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 0.041%, cationic charge demand 1.53 μ eq/g; Elongation at break 392%, recovery of elasticity number of times 12800 times.
Embodiment 5
Add succinic acid and 3 grams of octadecanoic acids of quality 90 grams, pass into nitrogen, mixed by mechanical stirring, be warmed up to 192 DEG C, keep mechanical stirring, 56 grams of 1-methylol-2-hydroxy-ethane potassium sulfonates are evenly dripped at 23min, then 202 DEG C are warmed up to, add 1.5 grams of antimony glycols, 135 grams of pentanediols are evenly dripped at 40min, be warmed up to 208 DEG C after pentanediol drips and continue reaction 17min, reduce the temperature to 192 DEG C, add 5 grams of carboxy nitrile rubbers, 4 grams of aqueous tackifier resins, 2 grams of paraffin, 4 grams of talcum powder, 0.3 gram of Tenox PG, mix and blend 10min cools, encapsulation.
The sizing agent cohesive strength 5.61MPa of preparation, melting viscosity 3.94Pas, softening temperature 94.2 DEG C, temperature limit of brittleness-4.3 DEG C, hardness 84.2; Normal temperature aqueous solubilities 99.3% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 0.051%, cationic charge demand 1.26 μ eq/g; Elongation at break 408%, recovery of elasticity number of times 14100 times.
Embodiment 6
Add succinic acid and 4 grams of octadecanoic acids of quality 130 grams, pass into helium, mixed by mechanical stirring, be warmed up to 194 DEG C, keep mechanical stirring, 55 grams of 1-methylol-2-hydroxy-ethane potassium sulfonates are evenly dripped at 20min, then 200 DEG C are warmed up to, add 1.5 grams of tetrabutyl titanates, 175 grams of pentanediols are evenly dripped at 40min, be warmed up to 208 DEG C after pentanediol drips and continue reaction 18min, reduce the temperature to 190 DEG C, add 4 grams of carboxy nitrile rubbers, 5 grams of aqueous tackifier resins, 2 grams of paraffin, 4 grams of talcum powder, 1 gram of Tenox PG, mix and blend 10min cools, encapsulation.
The sizing agent cohesive strength 5.51MPa of preparation, melting viscosity 4.52Pas, softening temperature 88.6 DEG C, temperature limit of brittleness-3.9 DEG C, hardness 83.1; Normal temperature aqueous solubilities 99.2% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 0.043%, cationic charge demand 1.55 μ eq/g; Elongation at break 390%, recovery of elasticity number of times 12800 times.
Embodiment 7
Add succinic acid and 3 grams of octadecanoic acids of quality 90 grams, pass into nitrogen, mixed by mechanical stirring, be warmed up to 192 DEG C, keep mechanical stirring, 56 grams of 1-methylol-2-hydroxy-ethane potassium sulfonates are evenly dripped at 23min, then 202 DEG C are warmed up to, add 1.5 grams of potassium fluotitanates, 135 grams of pentanediols are evenly dripped at 40min, be warmed up to 208 DEG C after pentanediol drips and continue reaction 17min, reduce the temperature to 192 DEG C, add 5 grams of carboxy nitrile rubbers, 4 grams of aqueous tackifier resins, 2 grams of paraffin, 4 grams of talcum powder, 0.3 gram of Tenox PG, mix and blend 10min cools, encapsulation.
The sizing agent cohesive strength 5.56MPa of preparation, melting viscosity 3.91Pas, softening temperature 94.1 DEG C, temperature limit of brittleness-4.1 DEG C, hardness 84.0; Normal temperature aqueous solubilities 99.1% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 0.053%, cationic charge demand 1.28 μ eq/g; Elongation at break 405%, recovery of elasticity number of times 14100 times.
Its cohesive strength of typical EVA hot-melt adhesive 4.67MPa of current double gummed paper bookbinding, melting viscosity 3.08Pas, softening temperature 78.4 DEG C, temperature limit of brittleness 2.1 DEG C, hardness 78.5; Normal temperature aqueous solubilities 36.5% (<3h), printing sheets reuse process is dissolved and colloidalmaterial (DCS) 3.21%, cationic charge demand 6.54 μ eq/g; Elongation at break 185%, recovery of elasticity number of times 7800 times, the present invention by comparison, its cohesive strength is improved obviously, and the dissolving of paper reuse process significantly reduces with colloidalmaterial (DCS) and strong ionic charge demand, waste paper is easy to size degradation, and reuse difficulty and cost reduce greatly, and wet end of machine efficiency is significantly improved.
Claims (7)
1. a double gummed paper preparation method for wetting ability adhesive bookbinding sizing agent, is characterized in that: comprise the following steps:
1) according to weight parts, by 50 ~ 150 parts of succinic acid and 1 ~ 5 part of octadecanoic acid mixing, stir, pass into rare gas element, be warming up to 188 ~ 194 DEG C, keep mechanical stirring;
2) drip 50 ~ 60 weight part 1-methylol-2-hydroxy-ethane potassium sulfonates, after dropwising, be warming up to 196 ~ 206 DEG C; The described 1-methylol of even dropping-2-hydroxy-ethane potassium sulfonate, and dropwise in 20 ~ 25min;
3) 1 ~ 3 weight part polycondensation catalyst is added;
4) drip 120 ~ 180 weight part pentanediols, after dropwising, be warming up to 208 ~ 216 DEG C, continue reaction 15 ~ 20min;
5) be cooled to 188 ~ 194 DEG C, add 1 ~ 3 weight part paraffin, 3 ~ 15 parts by weight binder, 2 ~ 6 parts by weight of filler, 0.1 ~ 1 weight part antioxidant, mix and stir, cooling.
2. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described polycondensation catalyst is antimony glycol.
3. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: evenly drip described pentanediol, and dropwise in 30 ~ 45min.
4. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described binding agent comprises 2 ~ 10 weight part carboxy nitrile rubbers, 1 ~ 5 weight part water-based tackifying resin.
5. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described weighting agent is talcum powder.
6. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described antioxidant is Tenox PG.
7. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described rare gas element is nitrogen.
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| CN201410170674.6A CN103937434B (en) | 2014-04-26 | 2014-04-26 | A kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent |
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| CN201410170674.6A CN103937434B (en) | 2014-04-26 | 2014-04-26 | A kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416456A (en) * | 2000-03-09 | 2003-05-07 | 阿托芬德利公司 | Sulfonated copolyester based water -dispersible hot melt adhesive |
| CN1621465A (en) * | 2003-10-02 | 2005-06-01 | 拜尔材料科学股份公司 | Aqueous composition for can coating |
| CN102250576A (en) * | 2011-06-09 | 2011-11-23 | 苏州瀚海化学有限公司 | Aqueous copolyester hot melt adhesive and preparation method thereof |
| CN102485821A (en) * | 2010-12-03 | 2012-06-06 | 北京博维特投资有限公司 | Adhesive and its preparation method |
| CN103160235A (en) * | 2012-04-17 | 2013-06-19 | 南京彤天广元高分子材料有限公司 | Resin powder bonding agent |
-
2014
- 2014-04-26 CN CN201410170674.6A patent/CN103937434B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416456A (en) * | 2000-03-09 | 2003-05-07 | 阿托芬德利公司 | Sulfonated copolyester based water -dispersible hot melt adhesive |
| CN1621465A (en) * | 2003-10-02 | 2005-06-01 | 拜尔材料科学股份公司 | Aqueous composition for can coating |
| CN102485821A (en) * | 2010-12-03 | 2012-06-06 | 北京博维特投资有限公司 | Adhesive and its preparation method |
| CN102250576A (en) * | 2011-06-09 | 2011-11-23 | 苏州瀚海化学有限公司 | Aqueous copolyester hot melt adhesive and preparation method thereof |
| CN103160235A (en) * | 2012-04-17 | 2013-06-19 | 南京彤天广元高分子材料有限公司 | Resin powder bonding agent |
Non-Patent Citations (2)
| Title |
|---|
| 水性聚酯的合成及性能研究进展;程万里等;《热固性树脂》;20090330;第24卷(第2期);56-59 * |
| 聚酯水性化技术及水性聚酯稳定性研究进展;刘身凯等;《化工进展》;20090805;第28卷(第8期);1376-1381 * |
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