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
At present invention 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 now research 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, with the research of the standby solid gums of other resin seldom, can suitability for industrialized production more rarely have report.Also researched and developed in addition some extraordinary solid gumss, such as the 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 all is opaque.Both at home and abroad about the report of transparent solid glue seldom, especially use the transparent solid glue of novel combination type alkaline soluble acrylic resin and novel excipient preparation more to have 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 traditional polyvinyl alcohol and the reaction product (polyvinyl formal) of formaldehyde is adhesive component, traditional sodium stearate is excipient, make pH adjusting agent although adopted potassium hydroxide, owing to can not fundamentally improve the mutual solubility with adhesive component, so the inevitable limited of the improvement of its transparency.Claim according to this patent: with the embodiment 1 solid gums sample with embodiment 14, respectively cut 1mm thickness sheet with its transmittance of spectrophotometric instrumentation, the transmittance of embodiment 14 solid gumss is 3 times of embodiment 1 under visible light.Although the transparency to solid gums increases, and still is 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 be the emulsion of using emulsifying agent to make, easy breakdown of emulsion, poor storage stability.So far yet there are no the solid gums with good transparency on the market.
Summary of the invention
First technical problem to be solved by this invention provides 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 provides 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 the 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, contain sulfonic group in the hydrophilic radical simultaneously, and adopt two kinds to have 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 an amount of, adopt sodium hydroxide solution to regulate the pH value, neutralization is 9~10 scopes to pH, can add an amount of sanitas (perhaps not adding) in the time of necessary, and water consumption is to supply 100 parts.
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 ℃ 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 ℃ of resin glass temperature.At room temperature to form suitable hydrogen bond between the molecule that guarantees these two kinds of resins and excipient, guarantee that the mixing physical efficiency that forms 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 an amount of bonding conditioning agent in case of necessity, and described bonding conditioning agent adopts polyvinylpyrrolidone.
Preferably, the mass concentration of described sodium hydroxide solution is 13~17%, is 9~10 scopes with its neutralization 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: in reactor, add alkaline soluble acrylic resin emulsion 1 and the alkaline soluble acrylic resin emulsion 2 of measuring, start stirring and be warmed up to 80~85 ℃, add in advance and dissolve good excipient Sorbitol dibenzal with solubility promoter, be 9~10 with the aqueous sodium hydroxide solution for preparing the in advance pH that neutralizes again, add wetting Agent for Printing Inks and when needing an amount of bonding conditioning agent that adds and other auxiliary agents such as (sanitas), the 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 more than are 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, contain sulfonic group in the hydrophilic radical 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 ℃ of resin glass temperature, the solid content of described alkaline soluble acrylic resin emulsion 2 is 40%, acid number 50mgKOH/g, 85 ℃ 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.
At last, 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 the alkaline soluble acrylic resin emulsion as tackiness agent, Sorbitol dibenzal is vehicle, having overcome traditional solid gums all is to do excipient with sodium stearate, bad with used adhesive component mutual solubility, the solid gums of producing does not have the shortcoming of the transparency, so that the solid gums of preparation not only has certain hardness and intensity, and the transparency is good, stability in storage is good, long quality-guarantee period, in the time of 60 ℃, do not melt trickling yet, to guarantee stored safely and the transportation of product, the 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 ℃ of resin glass temperature) 47 parts and alkaline soluble acrylic resin emulsion 2 (solid content 40%, acid number 50mgKOH/g, 85 ℃ of resin glass temperature) 4 parts, start stirring and be warmed up to 80~85 ℃, 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 the aqueous sodium hydroxide solution for preparing in advance (concentration approximately 15%) neutralization to pH again, add 8 parts of glycerine and 0.1 part of sanitas (adding the water polishing such as 100 parts of insufficient total amounts), in 82 ℃ of insulations 1 hour, stop to stir, left standstill filling bottle 1 hour.
Embodiment 2
In reactor, add alkaline soluble acrylic resin emulsion 1 (solid content 35%, acid number 80mgKOH/g, 15 ℃ of resin glass temperature) 43 parts and alkaline soluble acrylic resin emulsion 2 (solid content 40%, acid number 50mgKOH/g, 85 ℃ of resin glass temperature) 4 parts, 3 parts of PVP, start stirring and be warmed up to 80~85 ℃, 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 the aqueous sodium hydroxide solution for preparing in advance (concentration approximately 15%) neutralization to pH again, add 7.5 parts of glycerine and 0.1 part of sanitas (adding the water polishing such as 100 parts of insufficient total amounts), in 82 ℃ of insulations 1 hour, stop to stir, left standstill filling bottle 1 hour.
Embodiment 3
In reactor, add alkaline soluble acrylic resin emulsion 1 (solid content 35%, acid number 80mgKOH/g, 15 ℃ of resin glass temperature) 41 parts and alkaline soluble acrylic resin emulsion 2 (solid content 40%, acid number 50mgKOH/g, 85 ℃ of resin glass temperature) 10 parts, start stirring and be warmed up to 80~85 ℃, add 4 parts of Sorbitol dibenzals that dissolve with 15 parts of 1-oxyethyl groups-2-propyl alcohol in advance, be 10 with the aqueous sodium hydroxide solution for preparing in advance (concentration approximately 15%) neutralization to pH, add 8 parts of propylene glycol and 0.1 part of sanitas (adding the water polishing such as 100 parts of insufficient total amounts), in 82 ℃ of insulations 1 hour, stop to stir, left standstill filling bottle 1 hour.
The all technical of above-mentioned three embodiment all reaches QB/T 2857-2007 requirement, and product is transparent, and traditional solid gums has obvious difference.
Comparative Examples 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, be warmed up to 80~85 ℃ after the dissolving, add 8 parts of sodium stearate, add an amount of sanitas, it was 100 that water is regulated total amount, in 82 ℃ of insulations 1 hour, stop to stir, left standstill filling bottle 1 hour.Product is opaque.Other index conformance with standard requirement.
Comparative Examples 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 ℃, add 7 parts of sodium stearate, add an amount of sanitas, it is 100 that water is regulated total amount, in 82 ℃ of insulations 1 hour, stop stirring and left standstill filling bottle 1 hour.Product is opaque, contains free formaldehyde more than 0.1%, does not meet standard-required.
With the embodiment 3 solid gums sample with Comparative Examples 2, respectively cut 1mm thickness sheet, with its transmittance of spectrophotometric instrumentation, the transmittance of embodiment 3 solid gumss is 25 times of Comparative Examples 2 under visible light.After the solid gums of embodiment 3 preparation is cut into the 1mm thin slice, be placed on the newspaper, can be clear that its writing behind, whole glue rod also given the people obviously transparent sensation.