CN101220252B - Solid glue stick and method for producing the same - Google Patents
Solid glue stick and method for producing the same Download PDFInfo
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- CN101220252B CN101220252B CN2008100544857A CN200810054485A CN101220252B CN 101220252 B CN101220252 B CN 101220252B CN 2008100544857 A CN2008100544857 A CN 2008100544857A CN 200810054485 A CN200810054485 A CN 200810054485A CN 101220252 B CN101220252 B CN 101220252B
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Abstract
The invention discloses a solid glue stick, and is prepared with watercraft polyurethane latex as a major glue component, water as solvent, sodium stearate as gel, and polyvinyl alcohol and polyethylene pyrrole azululanone as accessory ingredients, and moderate glycerol added as humectant, wherein a self-emulsion method is adopted for the preparation of the watercraft polyurethane latex. The solid glue stick has the advantages that coated surface of the watercraft polyurethane adhesive adopted in preparing the solid glue stick is not easy to be damaged; the mechanical property is excellent; the modification is easy; the compatibility with paint is good; the prepared solid glue stick has obvious advantages in properties of assigned model, hardness, coating, and splicing, etc.; the appearance is pure white; the feeling is subtle; the splicing property is good; the drying speed is high; time for paper tearing is less than one minute; the hydrating period is as long as one year; the reserve property is fine.
Description
Technical field
The present invention relates to a kind of solid glue stick, being specifically related to a kind of is the solid glue stick of adhesive component with the aqueous polyurethane.
Background technology
Solid glue stick claims solid glue again, compares with liquid glue, and solid glue stick is not only easy to carry, and does not trickle, and is tack-free, and is therefore well received.The main raw material of solid glue stick is the paper product tackiness agent, and the material that adds some easy coagulation forming adds wetting Agent for Printing Inks, softening agent and flavouring agent again as gelifying agent, to improve the performance of aspects such as its use, storage, smell and outward appearance.Above-mentioned various raw materials by the lipstick formula packaging vessel internal cooling moulding of reinjecting through technology thorough mixing necessarily, after being uniformly dispersed of selected prescription, can be made solid glue stick.Make the solid glue stick of excellent property, key is to select proper raw material and auxiliary agent, and determines its optimum formula and reaction conditions, and wherein most important be exactly to select suitable tackiness agent.
As the main component of solid glue stick, the selection of tackiness agent is vital.Should select bonding force strong, glassware for drinking water is had strong dissemination or water-soluble, and the organic high molecular compound that is easy to be coated with out be as tackiness agent.Solid glue stick tackiness agent commonly used both at home and abroad at present has polyvinyl alcohol (PVA), Walocel MT 20.000PV, polyvinylpyrrolidone (PVP), polyvinyl formal, macromolecule resin mixture, starch, gelatine or gelatin etc.In these raw materials, the sticking paper effect of polyvinylpyrrolidone is fine, but not soluble in water, is soluble in organic solvent, makes its cost higher; Though it is starch, gelatine etc. are inexpensive, apt to deteriorate, not easy to store; With polyvinyl alcohol is that the glue rod quality that makes of raw material is fineless and smooth, has influenced the coating when using.
The exploitation of solid glue stick and development at first start from external, so far the history in year surplus in the of existing 70.Initial solid glue stick development is the solidification of liquid-type tackiness agent, allows tackiness agent use with solid-state form exactly.Along with the deepening continuously and develop of research, also regenerate bringing in constant renewal in as bonding tackiness agent.Through the development of decades, the research of external solid glue stick and utilisation technology be comparative maturity, the solid gums product-feed of the existing multiple trade mark of some companies.
Generally use polyvinyl alcohol and polyvinylpyrrolidone as tackiness agent in the world, the glue rod of making can provide enough physical strengths.On this basis, the someone utilizes water-soluble polymers as tackiness agent, and soap glue has been developed a kind of solid glue stick as excipient, has stronger adhesiveproperties and physical strength.Except main gel and gelifying agent, can also add the performance that some auxiliary agents improve solid glue stick.The kind aspect of external interpolation auxiliary agent is more domestic will be enriched manyly, and the every performance of therefore making of glue rod is also just more superior.The auxiliary agent of abroad using includes thickening material, sanitas, pigment, filler, essence, antioxidant, resin, dextrin, Mierocrystalline cellulose, starch derivative etc., wherein can use graphite, talcum, TiO
2, polymolecularity silicon soil, colloidal substance clay, silicon ore, chalk, magnesium oxide and glass fibre etc. be as pigment and filler.
A kind of solid glue stick that Germany develops, no matter all very superior on outward appearance or performance, this product appearance is transparent, the pure white exquisiteness of quality, hardness is moderate, and the time of just gluing is short, and bounding force is strong, stringiness and moisture retention are good, place after 1 year under the room temperature, still have very strong bonding force and moisture retention.
The research of domestic solid glue stick is started late, and development also relatively slowly.The present domestic tackiness agent of the various starting material of use as solid glue stick of mainly being devoted to study reaches best effects in the hope of the over-all properties that makes solid glue stick.
For example, though polyvinylpyrrolidone is fine as the tackiness agent effect of solid glue stick, not soluble in water, cost is higher, also is unfavorable for environmental protection simultaneously.Though the solid glue stick cost that uses polyvinyl alcohol-aqueous polyvinyl acetate emulsion to make is lower, but this type of glue rod quality is fineless and smooth, and period of storage is short, and (an about week) is just at the surface of glue rod formation thin film in the short period of time, influenced the use coating, practicality is little.Though with the water-soluble polymers one soap class solid agent of acyl acid anhydride base serves as that main to make the solid glue stick period of storage long, the time of just gluing is long, and cost is also high.
Duan Chengtian, Sun Yixiang (Shenyang chemical industry .1994, (3): 8-10) ternary complex with white glue with vinyl, the water-soluble polymers that contains acyl acid anhydride base and polyvinyl alcohol is a composite adhesive, the first sticking time and the period of storage of solid glue stick have been improved, owing to reduced the consumption that contains acyl acid anhydride based polyalcohol, also reduced the production cost of solid glue stick simultaneously.Yet although above three kinds of tackiness agent composite has certain synergy, the proportioning of ternary composite gum must be suitably, otherwise the three can not uniform mixing.Afterwards they in above-mentioned solid glue stick, added again new additive (Shenyang chemical industry .1995, (3): 12-13), with containing R-C in polyvalent alcohol and the molecular structure
6H
4-O
CH
2-CH
2-O
nThe compound of structure is composite as additive, has improved the solidifiability of solid agent, has reduced the viscosity of hot glue liquid, makes the hot glue magma water shaping easily, has brought very big convenience to production.But, the interpolation of new auxiliary is had higher requirement to proportion of raw materials again.
Cloudy peace (guizhou chemical industry .1998, (2): 22) developed a kind of new type of paper solid glue stick, the solid glue stick synthesis technique of making tackiness agent with gelatine or gelatin has been carried out exploring repeatedly, found a best process flow.Adopt gelatine and gelatin as tackiness agent, though cost of material is much lower than polyvinylpyrrolidone, water dispersible polymer resin and water-soluble or water dispersible synthetic resins etc., the solid glue stick of producing is apt to deteriorate, and is not easy to store.
The bright good fortune that continues (the natural science journal .1995 of Heilongjiang University, 12 (1): 110-113) with polyvinyl alcohol, carboxymethyl cellulose as tackiness agent, develop a kind of multifunctional solid glue rod.This solid adhesive adopts and makes based on the multiple industrial chemicals Compound Machining of macromolecular organic compound, and performance test shows characteristics such as having strong, the bonding time weak point of bonding force, stable performance, wide application.But the quality of this glue rod is fineless and smooth, has influenced the coating when using.
(chemistry world .1998 such as Chai Yuanwu, (6): 316-318) with the stearates be gelifying agent, polyvinyl acetate emulsion with polyvinyl alcohol modification is that tackiness agent prepares solid glue stick, tested the influence of gelifying agent, tackiness agent, solvent and wetting Agent for Printing Inks consumption with orthogonal experiment method, determined optimum formula and processing condition product performance.The solid glue stick bonding force of making is good, can reach paper-tear picture intensity in the 1min when gluing kraft paper, and paper fibre is destroyed when promptly peeling off, and glue-line does not come off.
In order further to improve the quality of products, reduce selling price, meet the need of market, many experts and technician adopt the tackiness agent of formaldehyde polyvinyl acetal water as solid glue stick by a large amount of experiments, and the glue rod of making not only viscosity is good, and the smooth exquisiteness of colloid, coating is evenly.
Li Mingrong (Tianjin chemical industry .1994, (3-4): be tackiness agent 17-18), jointly as forming agent, be developed into L-1 type solid glue stick with agar and sodium stearate with polyvinyl formal.The bonding force of this solid glue stick is good, and rate of drying is fast.(Chinese tackiness agent .2001 such as Chen Yonghong, 10 (3): 21-23) having studied with polyvinyl alcohol, formaldehyde, urea, sodium stearate etc. is prescription and the processing condition that main raw material prepares solid glue stick, the solid glue stick of producing is used for the bonding of various paper, all reach paper-tear picture intensity behind the 2min, after product was at room temperature placed 1 year naturally, every index was normal.(Henan chemical industry .2000 such as Hu Aizhu, (7): 11-12) on this basis, with the main body composition of polyacrylamide modified polyvinyl formal as tackiness agent, the sodium stearate that enrich in the source is as excipient, ethylene glycol is as wetting Agent for Printing Inks, and studied each component to the solid glue stick Effect on Performance, made better performances, cheap solid glue stick.The moon and equality (Zhejiang chemical industry .2005,36 (1): 23-25) with formaldehyde polyvinyl acetal water as tackiness agent, with sodium stearate as excipient, and in colloid, add various indicator, make the solid glue stick that is various bright-colored, the outward appearance exquisiteness, hardness is moderate, smear evenly and lubricate, bonding strength height and speed are fast.
But now commercially available solid glue stick still is that ubiquity that viscosity is low, the defective of stringiness and moisture retention difference, also exists a certain distance on embossability, package stability and some application performances.
Summary of the invention
The purpose of this invention is to provide a kind of novel solid glue stick, as tackiness agent, the solid glue stick adhesiveproperties of making is good with aqueous polyurethane for this solid glue stick, and rate of drying is fast.
A kind of preparation method of above-mentioned solid glue stick is provided, and is another goal of the invention of the present invention.
Solid glue stick of the present invention is to be the main gel composition with the aqueous polyurethane, water is solvent, adopts sodium stearate as gelifying agent, and polyvinyl alcohol and polyvinylpyrrolidone are auxiliary agent, and add that an amount of wetting Agent for Printing Inks glycerine makes, the weight percent of its each feed composition consists of:
Aqueous polyurethane emulsion 28～45%
Sodium stearate 7～12%
Water 30～45%
Glycerine 1～10%
Polyvinyl alcohol 0～8%
Polyvinylpyrrolidone 7～12%.
The preparation method of solid glue stick of the present invention is made up of three steps: the preparation of the preparation of aqueous polyurethane emulsion, the preparation of gelifying agent and solid glue stick.
Wherein self-emulsification is adopted in the preparation of aqueous polyurethane emulsion, and this method utilizes the wetting ability of himself to carry out emulsification by introduce hydrophilic radical on the urethane segment.This method does not add emulsifying agent, only relies on the hydrophilic radical of polyurethane structural to make it emulsification.Specifically can be divided into two stages: the fs is progressively polymerization in advance, promptly by in the end on the oligopolymer dibasic alcohol molecular chain-OH base and vulcabond (TDI) molecule-the NCO base according to certain amount than reaction, make the first aggressiveness of small molecules urethane of end-NCO base, in first aggressiveness, add wetting ability chainextender dimethylol propionic acid (DMPA) then and carry out chain extending reaction, on the distolateral base of polyurethane chain, introduce hydrophilic-COOH group, simultaneously owing to contain two-OH base in the DMPA molecule, can with first aggressiveness segment in-the further reaction of NCO base, thereby play the effect of chain extension, obtain molecular weight 10
3The aqueous polyurethane performed polymer of magnitude; Subordinate phase is the dispersion of performed polymer in water, in order to improve the dispersive ability in water of performed polymer, add the salt forming agent triethylamine in the performed polymer that in the fs, obtains and carry out neutralization reaction, make the pH value between 7～8, add water simultaneously and carry out high-speed stirring, emulsification pretreatment obtains aqueous polyurethane dispersion.
In the above-mentioned building-up reactions, it is main raw material that the present invention selects polyether Glycols N210 for use, is dispersion medium with the deionized water.At first with N210 at 0.05～0.07Mpa, vacuum hydro-extraction 2h under 110 ℃ of conditions is cooled to room temperature, according to n
NCO/ n
OH=2～2.5 amount of substance adds the proper catalyst dibutyl tin laurate again than add the TDI that measures in N210, is warming up to about 80～85 ℃ of isothermal reaction 0.5h.Be cooled to below 60 ℃, the DMPA that accounts for N210 and TDI total mass 5～6% is dissolved in an amount of N-Methyl pyrrolidone, join again in the reaction system, reacting about 1h about 75 ℃.Being cooled to about 40 ℃, under the high speed violent stirring, is 1: 1 consumption according to triethylamine and DMPA amount of substance ratio, slowly adding triethylamine aqueous solution emulsification disperses, continue to stir about 30min,, be polyether type aqueous polyaminoester emulsion up to obtaining uniform emulsion.
The preparation of gelifying agent sodium stearate is according to 6.5～7 among the present invention: 1 mass ratio is prepared stearic acid and sodium hydroxide, with dissolution of sodium hydroxide in water, neutralization reaction is carried out in adding stearic acid and heating, generates sodium stearate, as the gelifying agent (claiming excipient again) of solid glue stick.React as follows:
C
17H
35COOH+NaOH→C
17H
35COONa+H
2O
In the above-mentioned preparation process, the neutralization reaction time of stearic acid and sodium hydroxide is 30min, and the neutralization reaction temperature is 80～85 ℃, and the pH value of system is 8～9 behind the reaction terminating.
The preparation process of solid glue stick is actually a kind of simple physics uniform mixing process among the present invention, and chemical reaction does not take place between various raw materials and the auxiliary agent.Usually solid glue stick is that material by tackiness agent, gelifying agent and solvent three class difference in functionalitys constitutes, and adds an amount of auxiliary agent, to improve the performance of aspects such as its use, storage, smell and outward appearance.The present invention adopts aqueous polyurethane emulsion as tackiness agent, and sodium stearate is as gelifying agent, and water is as solvent, and glycerine, polyvinyl alcohol and polyvinyl pyrrolidone prepare solid glue stick as auxiliary agent.Aqueous polyurethane emulsion and sodium stearate do not react, and they can fuse composite, are suitable for making the glue rod.
Concrete technological process is take by weighing an amount of stearic acid solid heat fused in water-bath, and the adding suitable quantity of water to stir.In the time of 80～85 ℃, slowly add and calculate good NaOH solution, about stirring reaction 0.5h.The pH value of material is adjusted to about 8, adds load weighted preheating aqueous polyurethane emulsion, stirring and evenly mixing adds an amount of modified additive glycerine, polyvinyl alcohol and polyvinylpyrrolidone again, stirs to make it abundant mixing.Be cooled to about 60 ℃, pour the magma of heat into plastics tube container internal cooling and solidify with rotation push button, get final product solid glue stick.
The present invention is tackiness agent with the aqueous polyurethane emulsion, sodium stearate is a gelifying agent, and add suitable wetting Agent for Printing Inks and auxiliary agent prepares solid glue stick, since water-based polyurethane adhesive not easy damaged by coating surface, have the advantage that mechanical property is good, be easy to modification, and pollution-free, good with pigment compatibility, and over-all properties is superior, the solid glue stick of making all has tangible advantage on excipient, hardness, coating, performance such as bonding, have vast potential for future development and potentiality.
The production technique of solid glue stick of the present invention is simple, and the glue rod outward appearance that makes is pure white, the feel exquisiteness, and adhesiveproperties is good, and rate of drying is fast, and the paper-tear picture time, particularly the phase of preserving moisture reached 1 year less than 1min, and shelf characteric is good.
Embodiment
Embodiment 1
The preparation of aqueous polyurethane emulsion
Take by weighing the polyethers N210 of 100gMn=1000, pour in the four-hole boiling flask that agitator, prolong, thermometer are housed, in 0.05Mpa, 110 ℃ of about 2h of following vacuum hydro-extraction, cool to room temperature, add 35.5gTDI, add two catalyzer dibutyl tin laurates again, continue to be warming up to 85 ℃, isothermal reaction 0.5h.Be cooled to below 60 ℃, add the 20mLN-methyl-2-pyrrolidone solution that is dissolved with 7.5gDMPA, in about 75 ℃, react 1h.5.7g triethylamine and 230mL deionized water are mixed and made into triethylamine aqueous solution, under the high speed violent stirring, triethylamine aqueous solution are slowly added in the reaction system that is cooled to 40 ℃, behind the emulsification 30min, make solid content and be 45.3% aqueous polyurethane emulsion.
The preparation of solid glue stick
Take by weighing the 5.2g stearic acid, add and be equipped with in the four-hole boiling flask of whipping appts and condenser, in water-bath, be heated to about 70 ℃, stearic acid is melted fully.Add the 20mL deionized water, continue to be warming up to 80 ℃, slowly add the 10%NaOH solution of 8g, stirring reaction 0.5h is transferred to the pH value of material about 8.Add the aqueous polyurethane emulsion of 21g preheating, mix, add 5.4g glycerine again, the 5.3g polyvinylpyrrolidone stirs and makes it abundant mixing.Be cooled to about 60 ℃, regulate pH value to 8～9, pour the magma of heat into plastics tube container internal cooling curing, can obtain solid content and be 39.0% solid glue stick with rotation push button.
Embodiment 2
The preparation of aqueous polyurethane emulsion is with embodiment 1.
The preparation of solid glue stick
Take by weighing the 5.65g stearic acid, add and be equipped with in the four-hole boiling flask of whipping appts and condenser, in water-bath, be heated to 70 ℃, stearic acid is melted fully.Add the 19mL deionized water, continue to be warming up to 80 ℃, slowly add the 10%NaOH solution of 8.69g, stirring reaction 0.5h is transferred to the pH value of material about 8.Add the aqueous polyurethane emulsion of 26g preheating, mix, add 3.0g glycerine again, the 4.8g polyvinylpyrrolidone stirs and makes it abundant mixing.Be cooled to about 60 ℃, regulate pH value to 8～9, pour the magma of heat into plastics tube container internal cooling curing, can obtain solid content and be 51.83% solid glue stick with rotation push button.
Embodiment 3
The preparation of aqueous polyurethane emulsion
Take by weighing the polyethers N210 (Mn=1000) of 69.6g, pour in the four-hole boiling flask that agitator, prolong, thermometer are housed, in 0.06Mpa, 110 ℃ of about 2h of following vacuum hydro-extraction, cool to room temperature, add 24.3gTDI, add two catalyzer dibutyl tin laurates again, continue to be warming up to 85 ℃, isothermal reaction 0.5h.Be cooled to below 60 ℃, add the 15mLN-methyl-2-pyrrolidone solution that is dissolved with 5.25gDMPA, in about 75 ℃, react 1h.3.96g triethylamine and 160mL deionized water are mixed and made into triethylamine aqueous solution, under the high speed violent stirring, triethylamine aqueous solution are slowly added in the reaction system that is cooled to 40 ℃, behind the emulsification 30min, make solid content and be 45.4% aqueous polyurethane emulsion.
The preparation of solid glue stick
Take by weighing the 5g stearic acid, add and be equipped with in the four-hole boiling flask of whipping appts and condenser, in water-bath, be heated to 70 ℃, stearic acid is melted fully.Add the 15mL deionized water, continue to be warming up to 80 ℃, slowly add the 10%NaOH solution of 7.6g, stirring reaction 0.5h is transferred to the pH value of material about 8.Add the aqueous polyurethane emulsion of 22g preheating, mix, add 4.2g glycerine again, 6.7g polyvinylpyrrolidone and 3.3g polyvinyl alcohol stir and make it abundant mixing.Be cooled to about 60 ℃, regulate pH value to 8～9, pour the magma of heat into plastics tube container internal cooling curing, can obtain solid content and be 50.15% solid glue stick with rotation push button.
Embodiment 4
The preparation of aqueous polyurethane emulsion is with embodiment 3.
The preparation of solid glue stick
Take by weighing the 5.1g stearic acid, add and be equipped with in the four-hole boiling flask of whipping appts and condenser, in water-bath, be heated to 70 ℃, stearic acid is melted fully.Add the 23mL deionized water, continue to be warming up to 80 ℃, slowly add the 10%NaOH solution of 7.7g, stirring reaction 0.5h is transferred to the pH value of material about 8.Add the aqueous polyurethane emulsion of 20g preheating, mix, add 1.2g glycerine again, 6.7g polyvinylpyrrolidone and 4.8g polyvinyl alcohol stir and make it abundant mixing.Be cooled to about 60 ℃, regulate pH value to 8～9, pour the magma of heat into plastics tube container internal cooling curing, can obtain solid content and be 45.98% solid glue stick with rotation push button.
Embodiment 5
The preparation of aqueous polyurethane emulsion
Take by weighing the polyethers N210 (Mn=1000) of 66g, pour in the four-hole boiling flask that agitator, prolong, thermometer are housed, in 0.07Mpa, 110 ℃ of about 2h of following vacuum hydro-extraction, cool to room temperature, add 23gTDI, add two catalyzer dibutyl tin laurates again, continue to be warming up to 85 ℃, isothermal reaction 0.5h.Be cooled to below 60 ℃, add the 15mLN-methyl-2-pyrrolidone solution that is dissolved with 4.9gDMPA, in about 75 ℃, react 1h.3.7g triethylamine and 100mL deionized water are mixed and made into triethylamine aqueous solution, under the high speed violent stirring, triethylamine aqueous solution are slowly added in the reaction system that is cooled to 40 ℃, behind the emulsification 30min, make solid content and be 55% aqueous polyurethane emulsion.
The preparation of solid glue stick
Take by weighing the 5.1g stearic acid, add and be equipped with in the four-hole boiling flask of whipping appts and condenser, in water-bath, be heated to 70 ℃, stearic acid is melted fully.Add the 10mL deionized water, continue to be warming up to 85 ℃, slowly add the 10%NaOH solution of 7.7g, stirring reaction 0.5h is transferred to the pH value of material about 8.Add the aqueous polyurethane emulsion of 20g preheating, mix, add 1.8g glycerine again, 6.2g polyvinylpyrrolidone and 3.0g polyvinyl alcohol stir and make it abundant mixing.Be cooled to about 60 ℃, regulate pH value to 8～9, pour the magma of heat into plastics tube container internal cooling curing, can obtain solid content and be 54.27% solid glue stick with rotation push button.
Embodiment 6
The preparation of aqueous polyurethane emulsion is with embodiment 5.
The preparation of solid glue stick
Take by weighing the 5g stearic acid, add and be equipped with in the four-hole boiling flask of whipping appts and condenser, in water-bath, be heated to 70 ℃, stearic acid is melted fully.Add the 10mL deionized water, continue to be warming up to 85 ℃, slowly add the 10%NaOH solution of 7.65g, stirring reaction 0.5h is transferred to the pH value of material about 8.Add the aqueous polyurethane emulsion of 22g preheating, mix, add 3.4g glycerine again, the 3.75g polyvinylpyrrolidone stirs and makes it abundant mixing.Be cooled to about 60 ℃, regulate pH value to 8～9, pour the magma of heat into rotation push button plastics tube container internal cooling and solidify, can obtain solid glue stick, its solid content is 49.71%.
Claims (5)
1. the preparation method of a solid glue stick is to be the main gel composition with the aqueous polyurethane, and water is solvent, adopt sodium stearate as gelifying agent, polyvinyl alcohol and polyvinylpyrrolidone are auxiliary agent, and add an amount of wetting Agent for Printing Inks glycerine and make, and the weight percent of its each feed composition consists of:
It is characterized in that described preparation method is to prepare sodium stearate solution with stearic acid in the NaOH solution, the aqueous polyurethane emulsion that adds preheating, add modified additive glycerine, polyvinyl alcohol and polyvinylpyrrolidone again, stirring makes it abundant mixing, be cooled to 60 ℃, pour plastics tube container internal cooling into and solidify, obtain solid glue stick with rotation push button
Wherein, the solid content of described aqueous polyurethane emulsion is 55%.
2. the preparation method of solid glue stick according to claim 1 is characterized in that described polyaminoester emulsion adopts the self-emulsification preparation.
3. the preparation method of solid glue stick according to claim 2, the preparation that it is characterized in that described polyaminoester emulsion is the first aggressiveness of small molecules urethane that is made end-NCO base by polyether Glycols N210 and di-isocyanate reaction, add the chainextender dimethylol propionic acid again and carry out chain extending reaction, obtain the aqueous polyurethane performed polymer, in performed polymer, add the salt forming agent triethylamine and carry out neutralization reaction, add the water high-speed stirring simultaneously, emulsification pretreatment obtains aqueous polyurethane dispersion.
4. the preparation method of solid glue stick according to claim 3 is characterized in that the described triethylamine and the amount of substance ratio of dimethylol propionic acid are 1: 1.
5. the preparation method of solid glue stick according to claim 1, the preparation that it is characterized in that described sodium stearate be with stearic acid and sodium hydroxide with 6.5～7: 1 mass ratio reaction 0.5h, temperature of reaction is 80～85 ℃, system pH is 8～9 behind the reaction terminating.
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| CN102888975A (en) * | 2011-07-18 | 2013-01-23 | 东莞美哲塑胶制品有限公司 | Novel environment-friendly floor tile and manufacturing method thereof |
| CN104312501B (en) * | 2014-10-28 | 2016-06-29 | 浙江大学宁波理工学院 | A kind of preparation method of curry glue |
| KR101783089B1 (en) * | 2015-05-28 | 2017-09-28 | 이승엽 | Glue stick for document security process |
| CN105964882A (en) * | 2016-06-22 | 2016-09-28 | 马鞍山市创诚铸造有限公司 | Environment-friendly molding sand adopting cellulose sulfate modified animal glue as adhesive and preparation method thereof |
| CN108359402A (en) * | 2018-04-04 | 2018-08-03 | 江苏兴达文具集团有限公司 | Strength transparent solid glue material and preparation method thereof |
| CN108753237A (en) * | 2018-07-12 | 2018-11-06 | 淮北卓颂建筑工程有限公司 | A kind of building viscose material |
| KR102193210B1 (en) * | 2019-01-17 | 2020-12-18 | ㈜손안에세상 | Color Adhesive Composition |
| MX2022007234A (en) * | 2019-12-16 | 2022-07-12 | Henkel Ag & Co Kgaa | Dimensionally stable, wipe-on, modified polyether-polyurethane-ba sed adhesive compound. |
| CA3179492A1 (en) * | 2019-12-16 | 2021-06-24 | Henkel Ag & Co. Kgaa | Dimensionally stable, wipe-on, semi-crystalline polyester-based adhesive compound |
| CN111035800A (en) * | 2020-01-13 | 2020-04-21 | 昆明丰钰商贸有限责任公司 | Liquid band-aid containing aloe extract |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295603A (en) * | 1998-03-26 | 2001-05-16 | 汉高两合股份公司 | Soap gel based glue stick |
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2008
- 2008-01-25 CN CN2008100544857A patent/CN101220252B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295603A (en) * | 1998-03-26 | 2001-05-16 | 汉高两合股份公司 | Soap gel based glue stick |
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