A kind of transparent alkaline soluble acrylic resin solid gums and preparation method thereof
Technical field
The present invention relates to a kind of stationery, specifically a kind of transparent alkaline soluble acrylic resin solid gums and preparation method thereof.
Background technology
Invention at present and the practical solid gums of producing have two large classes, the first is made main binder constituents with modified polyvinyl alcohol (polyvinyl formal), its cohesiveness is low, shelf lives is short, easily gel, but cost is low, be still at present one of main products of domestic market, but owing to containing trace formaldehyde, do not meet environmental requirement, will be eliminated.Another kind of is the high adhesion solid gums of research now and production, and it is to make main binder constituents with polyvinylpyrrolidone (PVP), and its cohesiveness is high, temperature tolerance is good, shelf lives is long, but cost is relatively high, can become the principal item of domestic market in the future.Domestic except above-mentioned two large class solid gumss, little for the research of solid gums with other resin, can suitability for industrialized production more rarely have report.In addition also researched and developed some extraordinary solid gumss, as pressure-sensitive solid gums, allochroic solid and highly intense rapid drying solid gums etc.But all these products all use sodium stearate to do excipient, so outward appearance is all opaque.Little about the report of transparent solid glue both at home and abroad, the transparent solid glue that especially uses novel combination type alkaline soluble acrylic resin and novel excipient to prepare more has no report.For example number of patent application CN200910153831.1 is about a kind of environmentally-friendly transparent solid gums and preparation method, it adopts the reaction product (polyvinyl formal) of traditional polyvinyl alcohol and formaldehyde is adhesive component, traditional sodium stearate is excipient, make pH adjusting agent although adopted potassium hydroxide, owing to can not fundamentally improving and the mutual solubility of adhesive component, therefore the improvement of its transparency is inevitable quite limited.Claim according to this patent: the solid gums sample by embodiment 1 with embodiment 14, respectively cut its transmittance of 1mm thickness sheet spectrophotometric instrumentation, under visible ray, the transmittance of embodiment 14 solid gumss is 3 times of embodiment 1.Although the transparency to solid gums increases, and is still nowhere near.The patent No. is that CN20091009252.3 is about a kind of Emulsion acrylic resin solid gums, and it does not only have the transparency, owing to being the emulsion that uses emulsifying agent to make, and easily breakdown of emulsion, poor storage stability.So far on market, yet there are no the solid gums with good transparency.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of transparent alkaline soluble acrylic resin solid gums, not only has certain hardness and intensity, and transparent, long quality-guarantee period, stability in storage are good.
Second technical problem to be solved by this invention is to provide a kind of preparation method of transparent alkaline soluble acrylic resin solid gums.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: a kind of transparent alkaline soluble acrylic resin solid gums, it is characterized in that mainly adopting alkaline soluble acrylic resin emulsion is tackiness agent, Sorbitol dibenzal is vehicle, water is solvent, sodium hydroxide solution is neutralizing agent, alcohol ether is solubility promoter, and polyvalent alcohol is wetting Agent for Printing Inks;
Wherein the acid number of alkaline soluble acrylic resin emulsion is at 50~80mgKOH/g, with two or more hydrophilic radical, in hydrophilic radical, contain sulfonic group simultaneously, and adopt two kinds and there is different acid numbers and different second-order transition temperatures, with alkaline soluble acrylic resin emulsion 1 and the 2 conduct combinations of alkaline soluble acrylic resin emulsion of incomplete same hydrophilic and hydrophilic acidic group;
The mass fraction of each component is: alkaline soluble acrylic resin emulsion 1 is 40~50 parts, alkaline soluble acrylic resin emulsion 2 is 3~10 parts, 2~4 parts of vehicle, 10~20 parts of solubility promoters, 5~10 parts of wetting Agent for Printing Inkss, water and sodium hydroxide solution are appropriate, adopt sodium hydroxide solution to regulate pH value, neutralization is 9~10 scopes to pH, necessary time, can add appropriate sanitas (or not adding), and water consumption is to supply 100 parts, the mass fraction of water and sodium hydroxide solution is 4-40 part.
As preferably, described hydrophilic radical also comprises carboxyl, hydroxyl and amide group, and the solid content of described alkaline soluble acrylic resin emulsion 1 is 30~40%, acid number 70~80mgKOH/g, and, 15~20 DEG C of resin glass temperature; The solid content of described alkaline soluble acrylic resin emulsion 2 is 40~45%, acid number 40~50mgKOH/g, and, 85~95 DEG C of resin glass temperature.To ensure at room temperature to form suitable hydrogen bond between these two kinds of resins and the molecule of excipient, ensure that the mixing physical efficiency forming has required transparency and hardness.
Preferably, described solubility promoter adopts butoxy ethanol, 3-methoxyl group-3-butyl-n-butyl alcohol or 1-oxyethyl group-2-propyl alcohol.Can be used to increase the solvability of excipient Sorbitol dibenzal in water and the stability of solution, can use separately, preferably two or more mixes use, and these alcohol ethers also have moisturizing and lubrication simultaneously.
As improvement, described transparent alkaline soluble acrylic resin solid gums also comprises appropriate bonding conditioning agent if desired, and described bonding conditioning agent adopts polyvinylpyrrolidone.
Preferably, the mass concentration of described sodium hydroxide solution is 13~17%, with its neutralization be 9~10 scopes to pH.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: a kind of preparation method of transparent alkaline soluble acrylic resin solid gums, it is characterized in that: to the alkaline soluble acrylic resin emulsion 1 and the alkaline soluble acrylic resin emulsion 2 that add metering in reactor, start and stir and be warmed up to 80~85 DEG C, add the excipient Sorbitol dibenzal having dissolved with solubility promoter in advance, neutralizing pH with the aqueous sodium hydroxide solution preparing in advance is again 9~10, when adding wetting Agent for Printing Inks and need, the appropriate bonding conditioning agent adding and other auxiliary agents are as (sanitas), insulation certain hour, leave standstill, filling bottle, wherein alkaline soluble acrylic resin emulsion 1 is 40~50 parts, alkaline soluble acrylic resin emulsion 2 is 3~10 parts, 2~4 parts of vehicle, 10~20 parts of solubility promoters, 5~10 parts of wetting Agent for Printing Inkss, it is more than mass fraction.
As improvement, the acid number of described alkaline soluble acrylic resin emulsion 1 and alkaline soluble acrylic resin emulsion 2 is at 50~80mgKOH/g, with two or more hydrophilic radical, in hydrophilic radical, contain sulfonic group simultaneously, and both have different acid numbers and different second-order transition temperatures, with incomplete same hydrophilic and hydrophilic acidic group.
Preferably, the solid content of described alkaline soluble acrylic resin emulsion 1 is 35%, acid number 80mgKOH/g,, 15 DEG C of resin glass temperature, the solid content of described alkaline soluble acrylic resin emulsion 2 is 40%, acid number 50mgKOH/g, 85 DEG C of resin glass temperature.
Preferably, described solubility promoter adopts butoxy ethanol, 3-methoxyl group-3-butyl-n-butyl alcohol or 1-oxyethyl group-2-propyl alcohol.
Finally, described wetting Agent for Printing Inks adopts polyvalent alcohol, and described bonding conditioning agent adopts polyvinylpyrrolidone, and the mass concentration of described sodium hydroxide solution is 13~17%.
Compared with prior art, the invention has the advantages that: adopt alkaline soluble acrylic resin emulsion as tackiness agent, Sorbitol dibenzal is vehicle, having overcome traditional solid gums is all to do excipient with sodium stearate, bad with adhesive component mutual solubility used, the solid gums of producing does not have transparent shortcoming, make the solid gums of preparation not only there is certain hardness and intensity, and the transparency is good, stability in storage is good, long quality-guarantee period, in the time of 60 DEG C, do not melt trickling yet, to ensure stored safely and the transport of product, preparation method is simple simultaneously, easy to operate.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
In reactor, add alkaline soluble acrylic resin emulsion 1 (solid content 35%, acid number 80mgKOH/g, 15 DEG C of resin glass temperature) 47 parts and alkaline soluble acrylic resin emulsion 2 (solid content 40%, acid number 50mgKOH/g, 85 DEG C of resin glass temperature) 4 parts, start and stir and be warmed up to 80~85 DEG C, add in advance with 9 parts of butoxy ethanols and 3 parts of 3 parts of Sorbitol dibenzals that 3-methoxyl group-3-butyl-n-butyl alcohol dissolves, be 10 with aqueous sodium hydroxide solution (the concentration approximately 15%) neutralization preparing in advance to pH again, add 0.1 part of 8 parts of glycerine and sanitas (as 100 parts of polishings that add water of insufficient total amount), in 82 DEG C of insulations 1 hour, stop stirring, leave standstill 1 hour, filling bottle.
Embodiment 2
In reactor, add alkaline soluble acrylic resin emulsion 1 (solid content 35%, acid number 80mgKOH/g, 15 DEG C of resin glass temperature) 43 parts and alkaline soluble acrylic resin emulsion 2 (solid content 40%, acid number 50mgKOH/g, 85 DEG C of resin glass temperature) 4 parts, PVP3 part, start and stir and be warmed up to 80~85 DEG C, add in advance with 8 parts of 3-methoxyl group-3-butyl-n-butyl alcohols and 4 parts of 3 parts of Sorbitol dibenzals that 1-oxyethyl group-2-propyl alcohol dissolves, be 10 with aqueous sodium hydroxide solution (the concentration approximately 15%) neutralization preparing in advance to pH again, add 0.1 part of 7.5 parts of glycerine and sanitas (as 100 parts of polishings that add water of insufficient total amount), in 82 DEG C of insulations 1 hour, stop stirring, leave standstill 1 hour, filling bottle.
Embodiment 3
In reactor, add alkaline soluble acrylic resin emulsion 1 (solid content 35%, acid number 80mgKOH/g, 15 DEG C of resin glass temperature) 41 parts and alkaline soluble acrylic resin emulsion 2 (solid content 40%, acid number 50mgKOH/g, 85 DEG C of resin glass temperature) 10 parts, start and stir and be warmed up to 80~85 DEG C, add 4 parts of Sorbitol dibenzals that dissolve with 15 parts of 1-oxyethyl group-2-propyl alcohol in advance, neutralizing with the aqueous sodium hydroxide solution preparing in advance (concentration approximately 15%) is 10 to pH, add 0.1 part of 8 parts of propylene glycol and sanitas (as 100 parts of polishings that add water of insufficient total amount), in 82 DEG C of insulations 1 hour, stop stirring, leave standstill 1 hour, filling bottle.
The all technical of above-mentioned three embodiment all reaches QB/T2857-2007 requirement, and product is transparent, and traditional solid gums has obvious difference.
Comparative example 1 (general polyvinylpyrrolidone type solid gums)
In reactor, add 47 parts of water and 10 parts of glycerine, open stirring, add 22 parts of PVP K90s, after dissolving, be warmed up to 80~85 DEG C, add 8 parts of sodium stearate, add appropriate sanitas, it was 100 that water regulates total amount, in 82 DEG C of insulations 1 hour, stop stirring, leave standstill 1 hour, filling bottle.Product is opaque.Other index conformance with standard requirement.
Comparative example 2 (general polyvinyl formal type solid gums)
In reactor, add 72 parts of polyvinyl formals (solid content 12.5%) and 15 parts of glycerine, open stirring, be warmed up to 80~85 DEG C, add 7 parts of sodium stearate, add appropriate sanitas, it is 100 that water regulates total amount, in 82 DEG C of insulations 1 hour, stop stirring filling bottle standing 1 hour.Product is opaque, more than 0.1%, does not meet standard-required containing free formaldehyde.
Solid gums sample by embodiment 3 with comparative example 2, respectively cuts 1mm thickness sheet, and with its transmittance of spectrophotometric instrumentation, under visible ray, the transmittance of embodiment 3 solid gumss is 25 times of comparative example 2.Solid gums prepared by embodiment 3 is cut into after 1mm thin slice, is placed on newspaper, can be clear that its writing behind, and whole glue rod also given people obviously transparent sensation.