CN109517544A - A kind of environment-friendly type aqueous preparation method for pasting box glue and the product obtained by this method - Google Patents
A kind of environment-friendly type aqueous preparation method for pasting box glue and the product obtained by this method Download PDFInfo
- Publication number
- CN109517544A CN109517544A CN201811336992.XA CN201811336992A CN109517544A CN 109517544 A CN109517544 A CN 109517544A CN 201811336992 A CN201811336992 A CN 201811336992A CN 109517544 A CN109517544 A CN 109517544A
- Authority
- CN
- China
- Prior art keywords
- parts
- preparation
- monomer
- environment
- box glue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of preparation methods of environment-friendly type aqueous paste box glue, this method is that first tackifying resin is dissolved in acrylate monomer in acrylic emulsion preparation process, pre-emulsification and polymerization reaction are carried out together in company with acrylic monomers again, obtain the modified acrylic emulsion of tackifying resin, auxiliary agent is added dropwise in the modified acrylic emulsion of tackifying resin again, the pH value of lotion is adjusted to 6-8, viscosity 15000CPS-35000CPS, is obtained with 200 mesh filter screen filtrations;For the emulsifier that wherein pre-emulsification process uses for compound emulsifying agent, which is the mixture of anion emulsifier, nonionic emulsifier and reactive emulsifier, and the weight ratio of three is 1:1:1.Preparation method of the invention can avoid physical mixing bring inconsistent problem, and physical compounding method of taking refuge is due to needing to dissolve tackifying resin and bring organic solvent residual.The present invention also provides a kind of products obtained by above-mentioned preparation method.
Description
Technical field
The present invention relates to a kind of preparation of adhesive more particularly to a kind of preparations for pasting box glue, specifically relate to one kind
The preparation method of environment-friendly type aqueous paste box glue.The invention further relates to a kind of products that above-mentioned preparation method obtains.
Background technique
Paste box glue is also known as sealing compound or viscous box glue, is mainly used in printing industry post-press finishing production process, such as gift box
Paper, carton, the sealing of handbag, automatic box paster glue box, the mounting of bound book book case etc. automatically.Currently, existing paste on the market
Box glue mainly has two major classes: one kind is solvent type (mainly using toluene as solvent), and another kind of is Water emulsion (emulsion-type).20
The solvent type nineties in century pastes box glue using commonplace, but the attention with people to environmental protection, in addition export abroad is stringent
Limitation, solvent type are pasted box glue and are used by limitation, and the majority used currently on the market is that aqueous emulsion pastes box glue.
The existing paste box glue using acrylate as Water emulsion prepared by polymerized monomer always will appear in use
Disadvantages some in this way: (1) bonding force is not strong enough, and especially paper is poor to the ground bonding force of the difficult bonding such as PET, OPP;(2) resistance to height
Low temperature aging is undesirable.To improve cementability can and ageing-resistant performance, usually physical mixed adds in polyacrylate emulsion
Enter Tackified emulsion and crosslinking agent, because Tackified emulsion can effectively improve glue-line to the wetability of plastics, and then improves removing
Power, crosslinking agent can increase the cohesive strength of paste box glue-line, reduce influence of the temperature to glue-line peeling force.
The Chinese invention patent application of Publication No. CN107619647 discloses the environment-friendly type aqueous paste box adhesive of one kind
Preparation method, this method are that modifying cinepazid emulsion and rosin milk are put into mixing plant according to the ratio, with revolving speed 600-800 turn/
Point speed be stirred, then defoaming agent, moisturizer and wetting agent are added under stirring, continue stirring to being uniformly mixed,
Up to environment-friendly type aqueous paste box adhesive.The paste box glue that Tackified emulsion production is added in this physical compounding mode is still difficult to gram
The shortcomings that taking: (1) since Tackified emulsion and acrylic emulsion are simple physical mixeds, their compatibility is not place very well
In thermodynamic (al) metastable condition, it will lead to that compounding paste box glue storage stability is bad in this way, when also affecting engine sizing
Mechanical stability, namely particle is also easy to produce in gluing;(2) there are three types of Tackified emulsion production methods: room temperature reverses emulsion process, molten
Agent hydrotropy emulsion process and high temperature and pressure emulsion process.Room temperature reverses emulsion process to be only applicable to low softening point resin, and application range is small;It is molten
Agent hydrotropy emulsion process, with the presence of a small amount of solvent in product;High temperature and pressure emulsion process equipment requirement is high, and investment is big, and operation is not easy to slap
It holds, emulsifier needs high temperature resistant, at high cost.So the aqueous paste box glue surface of this preparation method production faces two problems, first is that VOC
It is not easy up to standard, environmental requirement is not met, second is that high expensive.
Summary of the invention
To solve the problems, such as present on, the object of the present invention is to provide a kind of preparation sides of environment-friendly type aqueous paste box glue
Method, the preparation method can avoid the limitation that physical compounding method generates, and make paste box glue obtained have tack good, when open
Between it is moderate, do not come unglued, high-low temperature resistant aging, TVOC meet paste box glue company standard.
The present invention also provides a kind of paste box glue obtained by above-mentioned preparation method.
In order to achieve the above object, the preparation method of environment-friendly type aqueous paste box glue of the invention, is prepared in acrylic emulsion
First tackifying resin is dissolved in acrylate monomer in the process, then carries out pre-emulsification and polymerization together instead in company with acrylic monomers
It answers, obtains the modified acrylic emulsion of tackifying resin, then auxiliary agent is added dropwise in the modified acrylic emulsion of tackifying resin, adjustment cream
The pH value of liquid is obtained to 6-8, viscosity 15000CPS-35000CPS with 200 mesh filter screen filtrations;Wherein pre-emulsification process is adopted
Emulsifier is compound emulsifying agent, which is anion emulsifier, nonionic emulsifier and reactive emulsifier
Mixture, the weight ratio of three is 1:1:1.
In above-mentioned preparation method, the anion emulsifier is selected from lauryl sodium sulfate, neopelex, alkane
Yl diphenyl ether disulfonate, positive decyl sodium sulphate, alkylol polyethers ammonium sulfate, sulfosuccinic acid alkyl alcohol ether ester sodium salt, sulfo group
One of succinic acid alkyl phenol ether ester sodium salt, alkylol polyethers sodium sulphate and polyoxyethylene ether (4) ammonium sulfate or in which a variety of
Combination;Nonionic emulsifier is in octylphenol ethoxylate, alcohol ethoxylate and nonyl phenol ethoxylate
One kind or in which a variety of combinations;Reactive emulsifier is selected from allyloxy nonylphenol polyethylene (10) ether ammonium sulfate, methyl
One in allyl hydroxide sodium dimercaptosulphanatein, sodium vinyl sulfonate, Sodium Allyl Sulfonate and 2- acrylamido -2- methyl propane sulfonic acid sodium
Kind or in which a variety of combinations.
Preferably, in the preparation method, acrylate monomer includes soft monomer, hard monomer, acid functional monomer and friendship
Receipts or other documents in duplicate body, above-mentioned tackifying resin are to be first dissolved in partial monosomy, then the pre-emulsification together with residual monomer, tackifying resin account for monomer
The 1-15% of total amount.
Preferably, in the preparation method, tackifying resin is selected from rosin, note alkene phenolic resin, α-note olefine resin or β-note
One of olefine resin or multiple combinations.
Preferably, in the preparation method, soft monomer is butyl acrylate and/or Isooctyl acrylate monomer;Hard monomer is second
Acetoacetic ester;Acid functional monomer is selected from one of acrylic acid, methacrylic acid and itaconic acid or a variety of combinations;Cross-linking monomer
Selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylamide, methyl
Acrylamide, N hydroxymethyl acrylamide, N- methylol methacrylamide, double acrylic acid glycol esters, divinylbenzene, third
One of olefin(e) acid ethylene oxidic ester, glycidyl methacrylate and N- fourth oxygen methacrylic acid or in which a variety of groups
It closes.
Preferably, in the preparation method, auxiliary agent includes pH adjusting agent, defoaming agent, wetting agent, thickener and preservative
One of or it is a variety of.
Preferably, above-mentioned preparation method, specifically comprises the following steps:
Then and 50- (1) 10-50 parts of tackifying resins: by weight, being first dissolved in 250-480 parts of soft monomers by pre-emulsification,
200 parts of hard monomers, 5-30 parts of acid functional monomers, 6-20 parts of cross-linking monomers, 0.5-2 parts of molecular weight regulators be added to by
In the emulsifier solution of 5-10 parts of compound emulsifying agents and 160 parts of deionized waters composition, stirring and emulsifying 30-35 minutes, pre- cream is obtained
Liquid;
(2) it polymerize: by weight, into the reaction vessel equipped with thermometer, blender, reflux condensing tube and constant pressure liquid water clock bucket
Pre-emulsion made from 200 parts of deionized waters, 0.5-1 parts of sodium bicarbonates and 5-20% step (1) is added, opens stirring, works as reaction
When material in container is warming up to 70-75 DEG C, the 20-40% of initiator solution is added, when the material in reaction vessel is warming up to
78-80 DEG C, when heat preservation does not flow back after twenty minutes, remaining pre-emulsion and initiator is added dropwise in continuous uniform in 3-4 hours
Solution is added dropwise, and is warming up to 85 DEG C, keeps the temperature 1-1.5 hours;Wherein initiator solution is that 2-5 parts of initiators are added 40 parts
In deionized water, stirring and dissolving is obtained;
(3) elimination of residual monomer: being cooled to 60-65 DEG C for the material after step (2) heat preservation, will preparatory prepared oxygen
Agent aqueous solution and reducing agent aqueous solution drop evenly in material in 1 hour simultaneously, and dropping temperature maintains 60-65 DEG C,
Then 40 DEG C are cooled to, 10-20 parts of pH adjusting agents, 1-3 parts of defoaming agents and 1-3 parts of wetting agents are added by weight and is stirred
Uniformly, the pH value of material is adjusted to 6-8, is discharged with 200 mesh filter screen filtrations, is obtained the modified acrylic emulsion of tackifying resin;
Wherein aqueous oxidizing agent solution is that 1 part of oxidant is dissolved in 10 parts of deionized waters to obtain, and reducing agent aqueous solution is by 1 part of reducing agent
10 parts of deionized waters are dissolved in obtain;
(4) the tackifying resin modified acrylic acid emulsion for obtaining 100 parts of steps (3) and 0.2-0.4 parts of defoaming agents, 0.1-0.2 parts
The mixing of wetting agent, 0.2-0.4 parts of fungicide, is eventually adding 0.3-1 part thickeners, adjusts viscosity to 15000CPS-35000CPS,
Environment-friendly type aqueous paste box glue is obtained with 200 mesh filter screen filtrations.
Preferably, in above-mentioned preparation method, the molecular weight regulator of step (1) is selected from n-dodecyl mercaptan, uncle 12
Alkyl hydrosulfide etc..
Preferably, in above-mentioned preparation method, the initiator of step (2) is selected from ammonium persulfate or potassium peroxydisulfate.
Preferably, in above-mentioned preparation method, the oxidant of step (3) is selected from tert-butyl hydroperoxide, hydrogen peroxide, over cure
Sour ammonium or potassium peroxydisulfate;Reducing agent is selected from ascorbic acid, FF6M or sodium hydrogensulfite.
Preferably, in above-mentioned preparation method, the wetting agent of step (3) and (4) is selected from Aerosol OT, fourth
Diacid di-isooctyl sodium sulfonate or acetylenic glycols nonionic surfactant.
Preferably, in above-mentioned preparation method, the defoaming agent of step (3) and (4) can be mineral oil or organic silicon defoaming
Agent.
The present invention also provides a kind of paste box glue obtained by above-mentioned preparation method, the glass transition temperature of the paste box glue-
10-- 50 DEG C, pH value 6-8, viscosity 15000CPS-35000CPS.
The preparation method of environment-friendly type aqueous paste box glue of the invention and the paste box glue of acquisition, have the advantage that
1, by the way that tackifying resin is dissolved in monomer in acrylic emulsion preparation process, pre-emulsification is carried out together in company with monomer
And polymerization reaction, contain the active double covalent bonds in part using tackifying resin, can be carried out instead with covalent double build on emulsion monomer
It answers, tackifying resin is grafted in acrylic body structure, not only make tackifying resin and acrylic resin by stable
It is chemically bound together, stability significantly improves, and avoiding physical mixing bring compatibility poorly causes machinery steady
Qualitative bad problem, and physical compounding method of taking refuge is due to needing to dissolve tackifying resin and bring organic solvent is residual
It stays.
2, during pre-emulsification, due to the addition of cross-linking monomer, after the acrylic emulsion for keeping tackifying resin modified is dry
Glue-line is cross-linked into network-like structure, and cohesive force greatly improves, high and low temperature resistance enhancing, and ageing-resistant performance is excellent;And use second
Vinyl acetate can provide cohesive strength as hard monomer, to improve the viscosity of holding of glue, and vinyl acetate cost compares first
Base methyl acrylate is obviously low.
3, emulsifier is compounded using anion emulsifier, nonionic emulsifier and reactive emulsifier, existing yin from
The electric double layer protective effect of son, and have non-ionic steric hindrance protective effect, the synergistic effect of the two makes polymerization stability
More preferably, the low bubble of reactive emulsifier and the copolymerization that can participate in monomer is also just not present there is no migration is easy
The weak interface layer between glue and ground is generated, the bonding force of transfer adhesive is improved, makes pasted paper to PET film, OPP film stripping power
It is improved.
4, preparation method of the invention, simple process are achieved that using the production equipment of existing acrylic emulsion, are obtained
Paste box glue can adapt to the craft of various gift boxes, carton etc. or the production of machine paste box, have that tack is good, the open hour
It is moderate, do not come unglued, high-low temperature resistant aging the characteristics of, TVOC meet paste box glue company standard.
Specific embodiment
Technical scheme of the present invention will be further described combined with specific embodiments below, but these embodiments are not used
To limit the scope of the invention, under the premise of not departing from theory of the present invention, small change to preparation process process conditions,
It is within the scope of protection of the invention.
One, product embodiments
Embodiment 1
1. the preparation of tackifying resin modified acrylic acid emulsion
(1) preparation of pre-emulsion: by weight, first 50 parts of rosin are dissolved in 320 parts of butyl acrylates (stirring and dissolving), so
Afterwards with 150 parts of vinyl acetates, 15 parts of acrylic acid, 15 parts of hydroxy-ethyl acrylates, 0.7 part of n-dodecyl mercaptan is added to by 5
Part lauryl sodium sulfate, 5 parts of nonyl phenol ethoxylates (CO630), 5 parts of allyloxy nonylphenol polyethylenes (DNS86) and
In the emulsifier solution of 160 parts of deionized waters composition, stirs fully emulsified 30 minutes, pre-emulsion is made;
(2) by weight, 3 parts of ammonium persulfates are added in 40 parts of deionized waters, stirring dissolves initiator, and it is molten to obtain initiator
Liquid;
(3) preparation of lotion: by weight, to the reaction that thermometer, blender, reflux condensing tube and constant pressure liquid water clock bucket are housed
200 parts of deionized waters, 0.5 part of sodium bicarbonate and step (1) are added in container and obtains the 10% of pre-emulsion, and opens stirring;When anti-
When the material in container being answered to be warming up to 72 DEG C, the 30% of initiator solution is added;When the material in reaction vessel is warming up to 78-80
DEG C, when heat preservation does not flow back after twenty minutes, remaining pre-emulsion and initiator solution is added dropwise in 3-4 hours continuous uniforms, is added dropwise
It finishes, is warming up to 85 DEG C, keep the temperature 1 hour;
(4) by weight, 10 parts of deionized waters being added in 1 part of tert-butyl hydroperoxide, stirring dissolves tert-butyl hydroperoxide,
Aqueous oxidizing agent solution is obtained, 10 parts of deionized waters are added in 1 part of reducing agent ascorbic acid, stirring keeps reducing agent ascorbic acid molten
Solution, obtains reducing agent aqueous solution;
(5) elimination of residual monomer: being cooled to 60-65 DEG C after heat preservation, by the tertiary aqueous oxidizing agent solution being pre-equipped with and also
Former agent aqueous solution drops evenly in lotion in 1 hour, is then cooled to 40 DEG C, and 10 parts of mass concentrations are added by weight and are
25% ammonium hydroxide, 1 part of defoaming agent 825 and 1 part wetting agent GPG are simultaneously stirred evenly, and adjust pH value to 6-7, with 200 mesh filter screen mistakes
Material is filtered out, the modified acrylic emulsion of tackifying resin is obtained.
2, the preparation of environment-friendly type paste box glue
The modified acrylic emulsion of 100 parts of above-mentioned tackifying resins is put into impregnation cylinder, 0.2-0.4 parts of addition disappears after starting stirring
GPG and 0.2-0.4 parts of isothiazolinone of infusion 825,0.1-0.2 parts of wetting agents, stir evenly, are eventually adding 0.3-1 parts of poly- ammonia
Ester thickener, adjustment viscosity, with 200 mesh filter screen filtrations, obtain environment-friendly type aqueous paste box to 15000CPS-35000CPS qualification
Glue.
Embodiment 2
1. the preparation of tackifying resin modified acrylic acid emulsion
(1) preparation of pre-emulsion: by weight, 30 parts of terpene phenol resins are first dissolved in 90 parts of butyl acrylates and 200 part third
In the different monooctyl ester of olefin(e) acid, then with 200 parts of vinyl acetates, 15 parts of methacrylic acids, 15 parts of glycidyl methacrylate
(GMA), 0.5 part of n-dodecyl mercaptan is added to by 5 parts of alkyl diphenyl ether disulfonates (2A1), 5 parts of nonyl phenol ethoxylations
In the emulsifier solution of object (CO630), 5 parts of sodium vinyl sulfonates and 160 parts of deionized waters composition, stirring and emulsifying 30 minutes, system
At pre-emulsion;
(2) by weight, 3 parts of ammonium persulfates are added in 40 parts of deionized waters, stirring dissolves initiator, and it is molten to obtain initiator
Liquid;
(3) preparation of lotion: by weight, to the reaction that thermometer, blender, reflux condensing tube and constant pressure liquid water clock bucket are housed
200 parts of deionized waters, 0.5 part of sodium bicarbonate and step (1) are added in container and is prepared the 10% of pre-emulsion, and opens stirring;
When the material in reaction vessel is warming up to 72 DEG C, the 30% of initiator solution is added;When the material in reaction vessel is warming up to
78-80 DEG C, when heat preservation does not flow back after twenty minutes, remaining pre-emulsion is added dropwise in 3-4 hours continuous uniforms and initiator is molten
Liquid is added dropwise, and is warming up to 85 DEG C, keeps the temperature 1 hour;
(4) by weight, 10 parts of deionized waters being added in 1 part of tert-butyl hydroperoxide, stirring dissolves tert-butyl hydroperoxide,
Aqueous oxidizing agent solution is obtained, 10 parts of deionized waters are added in 1 part of reducing agent ascorbic acid, stirring keeps reducing agent ascorbic acid molten
Solution, obtains reducing agent aqueous solution;
(5) elimination of residual monomer: being cooled to 60-65 DEG C after heat preservation, by the aqueous oxidizing agent solution being pre-equipped with and reduction
Agent aqueous solution drops evenly in material in 1 hour simultaneously, is then cooled to 40 DEG C, and 10 parts of mass concentrations are added by weight
25% ammonium hydroxide, 1 part of DF-7015 mineral oil antifoam agent and 1 part of OT-75 wetting agent, and stir evenly, pH value is adjusted to 6-7, is used
The discharging of 200 mesh filter screen filtrations obtains the modified acrylic emulsion of tackifying resin.
2, the preparation of environment-friendly type paste box glue
By in the modified acrylic emulsion investment impregnation cylinder of 100 parts of above-mentioned tackifying resins, 0.2-0.4 parts are added after starting stirring
DF-7015 mineral oil antifoam agent, 0.1-0.2 parts of OT-75 wetting agents and 0.2-0.4 parts of isothiazolinone, stir evenly, finally plus
Enter 0.3-1 parts of polyurethane thickeners, adjustment viscosity, with 200 mesh filter screen filtrations, is obtained to 15000CPS-35000CPS qualification
Environment-friendly type aqueous paste box glue.
Embodiment 3
1. the preparation of tackifying resin modified acrylic acid emulsion
(1) preparation of pre-emulsion: by weight, 70 parts of terpene phenol resins are first dissolved in 90 parts of butyl acrylates and 160 part third
In the different monooctyl ester of olefin(e) acid, then it is added with 200 parts of vinyl acetates, 15 parts of itaconic acids, 15 parts of GMA, 0.5 part of n-dodecyl mercaptan
To by 5 parts of polyoxyethylene ether (4) ammonium sulfate (CO436), 5 parts of nonyl phenol ethoxylates (CO630), 5 parts of Sodium Allyl Sulfonate
In the emulsifier solution of 160 parts of deionized waters composition, stirring and emulsifying 30 minutes, pre-emulsion is made;
(2) by weight, 3 parts of ammonium persulfates are added in 40 parts of deionized waters, stirring dissolves initiator, and it is molten to obtain initiator
Liquid;
(3) preparation of lotion: by weight, to the reaction that thermometer, blender, reflux condensing tube and constant pressure liquid water clock bucket are housed
200 parts of deionized waters, 0.5 part of sodium bicarbonate and step (1) are added in container and prepares the 10% of pre-emulsion, and opens stirring;When anti-
When the material in container being answered to be warming up to 72 DEG C, the 30% of initiator solution is added;When the material in reaction vessel is warming up to 78-80
DEG C, when heat preservation does not flow back after twenty minutes, remaining pre-emulsion and initiator solution is added dropwise in 3-4 hours continuous uniforms, is added dropwise
It finishes, is warming up to 85 DEG C, keep the temperature 1 hour;
(4) by weight, 10 parts of deionized waters are added in 1 part of tert-butyl hydroperoxide, stirring keeps tert-butyl hydroperoxide molten
Solution, obtains aqueous oxidizing agent solution, 10 parts of deionized waters is added in 1 part of reducing agent FF6M, stirring is dissolved reducing agent FF6M, obtained
Reducing agent aqueous solution;
(5) 60-65 DEG C the elimination of residual monomer: is cooled to after heat preservation by the aqueous oxidizing agent solution being pre-equipped with and containing reduction
Agent aqueous solution drops evenly in lotion in 1 hour, is then cooled to 40 DEG C, and 10 parts of mass concentrations are added by weight and are
25% ammonium hydroxide, 1 part of DF-7015 mineral oil antifoam agent and 1 part of OT-75 wetting agent simultaneously stir evenly, and adjust pH value to 6-7, use
The discharging of 200 mesh filter screen filtrations obtains the modified acrylic emulsion of tackifying resin.
2, the preparation of environment-friendly type paste box glue
By in the modified acrylic emulsion investment impregnation cylinder of 100 parts of above-mentioned tackifying resins, 0.2-0.4 parts are added after starting stirring
DF-7015 mineral oil antifoam agent, 0.1-0.2 parts of OT-75 wetting agents and 0.2-0.4 parts of isothiazolinone, stir evenly, finally
0.3-1 parts of polyurethane thickeners are added, adjustment viscosity, with 200 mesh filter screen filtrations, is obtained to 15000CPS-35000CPS qualification
To environment-friendly type aqueous paste box glue.
Two, comparative example
It by the formula of embodiment 1, is added without tackifying resin and Conventional acrylic lotion is made, then Tackified emulsion is pressed into acrylic emulsion
The ratio of 10-30%, which is added in above-mentioned Conventional acrylic lotion, produces paste box glue according to paste box glue preparation process.
Three, properties of product are tested
Performance test methods:
1, tack
(1) paper to be stained with is torn into the small rectangle of centimeter length, inner meter Kuan great;(2) by the wherein one side of coincidence after doubling
It is uniform to apply gluing, start timing;(3) foldable plane is gently pressed with thumb and index finger, two coincidence faces are not because glue has at the beginning
It is just viscous
Property is easy for flick.
(4) repeat step (3) movement, foldable planes bonding waited not flick, timing terminates, be exactly in this period tack when
Between.
2, the detection of adhesive strength
24 hours detection adhesive strengths after paste box adhesive paste box tear adhesive surface along paste pod interface, if paper interface facial tissue is fine
70% or more dimension is torn, then adhesive strength is considered qualified.
3, heat resistance
The box pasted is put into 60 DEG C, in the baking oven of relative humidity 70 ± 5%, the interface of 72 hours back boxs is placed, is not bubbled,
It does not come unglued, is peeled away along interface, be greater than 70% paper fiber and destroy.
4、TVOC
TVOC test: it is respectively coated with (No. 6 bars) 3g paste box glue using the two-sided art paper of 2 A4 areas, after waiting dry tack free
It is placed in the sealed bag of A4 size (more than 8 thickness) and seals, be placed in 40 DEG C of baking ovens 30 minutes, taking-up etc. to be cooled 15
TVOC content in sealed bag is measured with the ppbRAE 3000 of RAE company after minute, being as a result no more than 15ppm is qualification.
5, mechanical stability
The 200g lotion of 120 mesh net filtrations is added in the enamelled cup of 1000ml, enamelled cup is placed on blender, uses
Clip is fixed, and stirring is started, and is turned speed to 4000r/min, is stirred 0.5 hour, and whether observation lotion is demulsified or flocculates, and does not have such as
Obvious flocculate, then with 120 mesh net filtrations, think to pass through if having no or only minute quantity flocculate.
Performance detection is carried out to product made from embodiment 1-3 and comparative example using the above method, as a result as follows:
The present invention is by being dissolved in list for tackifying resin in acrylic emulsion preparation process it can be seen from above-mentioned testing result
In body, the paste box glue that pre-emulsification and polymerization reaction obtain, the tack having had and heat resistance are carried out together in company with monomer, and are shelled
The product obtained using physical mixed is substantially better than from indexs such as intensity, mechanical stability and TVOC.
Claims (10)
1. a kind of preparation method of environment-friendly type aqueous paste box glue, is first to dissolve tackifying resin in acrylic emulsion preparation process
Pre-emulsification and polymerization reaction are carried out together in acrylate monomer, then in company with acrylic monomers, obtain what tackifying resin was modified
Acrylic emulsion, then auxiliary agent is added dropwise in the modified acrylic emulsion of tackifying resin, pH value to 6-8, the viscosity for adjusting lotion is
15000CPS-35000CPS is obtained with 200 mesh filter screen filtrations;The emulsifier that wherein pre-emulsification process uses is composite emulsifying
Agent, the compound emulsifying agent are the mixture of anion emulsifier, nonionic emulsifier and reactive emulsifier, the weight ratio of three
For 1:1:1.
2. the preparation method of environment-friendly type aqueous paste box glue according to claim 1, it is characterised in that: described anionic emulsifying
Agent is selected from lauryl sodium sulfate, neopelex, alkyl diphenyl ether disulfonate, positive decyl sodium sulphate, alkylol
Polyethers ammonium sulfate, sulfosuccinic acid alkyl alcohol ether ester sodium salt, sulfosuccinic acid alkyl phenol ether ester sodium salt, alkylol polyethers sodium sulphate
With one of polyoxyethylene ether (4) ammonium sulfate or in which a variety of combinations;Nonionic emulsifier is selected from octyl phenol ethoxylation
One of object, alcohol ethoxylate and nonyl phenol ethoxylate or in which a variety of combinations;Reactive emulsifier choosing
From allyloxy nonylphenol polyethylene (10) ether ammonium sulfate, methallyl hydroxide sodium dimercaptosulphanatein, sodium vinyl sulfonate, allyl sulphonic acid
One of sodium and 2- acrylamido -2- methyl propane sulfonic acid sodium or in which a variety of combinations.
3. the preparation method of environment-friendly type aqueous paste box glue according to claim 1 or 2, it is characterised in that: the acrylic acid
Ester monomer includes soft monomer, hard monomer, acid functional monomer and cross-linking monomer, and above-mentioned tackifying resin is to be first dissolved in partial monosomy
In, then the pre-emulsification together with residual monomer, tackifying resin account for the 1-15% of monomer total amount.
4. the preparation method of environment-friendly type aqueous paste box glue according to claim 3, it is characterised in that: it is characterized by: institute
It states tackifying resin and is selected from the rosin series resins, note alkene phenolic resin such as rosin, hydrogenated rosin, disproportionated rosin, alkyl phenol resin,
One of C5/C9 Petropols, xylene resin, α-note olefine resin or β-note olefine resin or multiple combinations, soft monomer third
Olefin(e) acid butyl ester and/or Isooctyl acrylate monomer.
5. the preparation method of environment-friendly type aqueous paste box glue according to claim 4, it is characterised in that: the hard monomer is second
Acetoacetic ester;Acid functional monomer is selected from one of acrylic acid, methacrylic acid and itaconic acid or a variety of combinations;Cross-linking monomer
Selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylamide, methyl
Acrylamide, N hydroxymethyl acrylamide, N- methylol methacrylamide, double acrylic acid glycol esters, divinylbenzene, third
One of olefin(e) acid ethylene oxidic ester, glycidyl methacrylate and N- fourth oxygen methacrylic acid or in which a variety of groups
It closes.
6. the preparation method of environment-friendly type aqueous paste box glue according to claim 5, it is characterised in that: the auxiliary agent includes pH
It is worth one of regulator, defoaming agent, wetting agent, thickener and preservative or a variety of.
7. the preparation method of environment-friendly type aqueous paste box glue according to claim 6, it is characterised in that: the preparation method tool
Body includes the following steps:
Then and 50- (1) 10-50 parts of tackifying resins: by weight, being first dissolved in 250-480 parts of soft monomers by pre-emulsification,
200 parts of hard monomers, 5-30 parts of acid functional monomers, 6-20 parts of cross-linking monomers, 0.5-2 parts of molecular weight regulators be added to by
In the emulsifier solution of 5-10 parts of compound emulsifying agents and 160 parts of deionized waters composition, stirring and emulsifying 30-35 minutes, pre- cream is obtained
Liquid;
(2) it polymerize: by weight, into the reaction vessel equipped with thermometer, blender, reflux condensing tube and constant pressure liquid water clock bucket
Pre-emulsion made from 200 parts of deionized waters, 0.5-1 parts of sodium bicarbonates and 5-20% step (1) is added, opens stirring, works as reaction
When material in container is warming up to 70-75 DEG C, the 20-40% of initiator solution is added, when the material in reaction vessel is warming up to
78-80 DEG C, when heat preservation does not flow back after twenty minutes, remaining pre-emulsion and initiator is added dropwise in continuous uniform in 3-4 hours
Solution is added dropwise, and is warming up to 85 DEG C, keeps the temperature 1-1.5 hours;Wherein initiator solution is that 2-5 parts of initiators are added 40 parts
In deionized water, stirring and dissolving is obtained;
(3) elimination of residual monomer: being cooled to 60-65 DEG C for the material after step (2) heat preservation, will preparatory prepared oxygen
Agent aqueous solution and reducing agent reducing agent aqueous solution drop evenly in material in 1 hour simultaneously, are then cooled to 40 DEG C, press
Poidometer is added 10-20 parts of pH adjusting agents, 1-3 parts of defoaming agents and 1-3 parts of wetting agents and stirs evenly, and adjusts the pH of material
Value is discharged with 200 mesh filter screen filtrations to 6-8, obtains the modified acrylic emulsion of tackifying resin;Wherein aqueous oxidizing agent solution
It is that 1 part of oxidant is dissolved in 10 parts of deionized waters to obtain, reducing agent aqueous solution is that 1 part of reducing agent is dissolved in 10 parts of deionizations
Water obtains;
(4) the tackifying resin modified acrylic acid emulsion for obtaining 100 parts of steps (3) and 0.2-0.4 parts of defoaming agents, 0.1-0.2 parts
The mixing of wetting agent, 0.2-0.4 parts of fungicide, is eventually adding 0.3-1 part thickeners, adjusts viscosity to 15000CPS-35000CPS,
Environment-friendly type aqueous paste box glue is obtained with 200 mesh filter screen filtrations.
8. the preparation method of environment-friendly type aqueous paste box glue according to claim 7, it is characterised in that: the step (1)
Molecular weight regulator is selected from n-dodecyl mercaptan, tert-dodecylmercaotan etc..
9. the preparation method of environment-friendly type aqueous paste box glue according to claim 8, it is characterised in that: the step (3)
Oxidant is selected from tert-butyl hydroperoxide, hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate;Reducing agent is selected from ascorbic acid, FF6M
Or sodium hydrogensulfite.
10. a kind of paste box glue obtained by any preparation method of claim 1-9, the glass transition temperature of the paste box glue-
10-- 50 DEG C, pH value 6-8, viscosity 15000CPS-35000CPS.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811336992.XA CN109517544B (en) | 2018-11-12 | 2018-11-12 | Preparation method of environment-friendly water-based box paste glue and product obtained by method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811336992.XA CN109517544B (en) | 2018-11-12 | 2018-11-12 | Preparation method of environment-friendly water-based box paste glue and product obtained by method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109517544A true CN109517544A (en) | 2019-03-26 |
CN109517544B CN109517544B (en) | 2021-06-11 |
Family
ID=65776289
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811336992.XA Active CN109517544B (en) | 2018-11-12 | 2018-11-12 | Preparation method of environment-friendly water-based box paste glue and product obtained by method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109517544B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111100522A (en) * | 2019-12-26 | 2020-05-05 | 万华化学集团股份有限公司 | Interior wall coating with lasting fragrance and preparation method thereof |
CN111187586A (en) * | 2020-01-21 | 2020-05-22 | 江苏景宏新材料科技有限公司 | Ultra-high viscosity acrylate emulsion pressure-sensitive adhesive and preparation method thereof |
CN114958243A (en) * | 2022-06-30 | 2022-08-30 | 浙江冠豪新材料有限公司 | Pressure-sensitive adhesive label and preparation method thereof |
CN117903683A (en) * | 2024-01-17 | 2024-04-19 | 中山市鑫峰光固化材料有限公司 | Soft light water-based light-cured coating and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1651541A (en) * | 2004-02-06 | 2005-08-10 | 上海东和胶粘剂有限公司 | Water resistant aqueous adhesion agent |
CN102603957A (en) * | 2012-02-29 | 2012-07-25 | 长兴化学工业(中国)有限公司 | Water-based adhesive component and preparation method of water-based pressure sensitive adhesive formed by water-based adhesive component |
CN104910838A (en) * | 2015-06-05 | 2015-09-16 | 华南理工大学 | Emulsion-type polyacrylate pressure-sensitive adhesive, and preparation method and application thereof |
KR20160011683A (en) * | 2016-01-12 | 2016-02-01 | 주식회사 엘지화학 | Method of Producing Acrylic Emulsion Comprising Tackifier |
CN105623561A (en) * | 2016-03-25 | 2016-06-01 | 江南大学 | Paper flocking adhesive and preparation method thereof |
CN108084927A (en) * | 2016-11-19 | 2018-05-29 | 辽宁东夫材料科技有限公司 | A kind of water soluble acrylic acid adhesive and preparation method thereof |
CN108410398A (en) * | 2018-04-04 | 2018-08-17 | 常州五荣化工有限公司 | A kind of preparation method of emulsion acrylate contact adhesive |
-
2018
- 2018-11-12 CN CN201811336992.XA patent/CN109517544B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1651541A (en) * | 2004-02-06 | 2005-08-10 | 上海东和胶粘剂有限公司 | Water resistant aqueous adhesion agent |
CN102603957A (en) * | 2012-02-29 | 2012-07-25 | 长兴化学工业(中国)有限公司 | Water-based adhesive component and preparation method of water-based pressure sensitive adhesive formed by water-based adhesive component |
CN104910838A (en) * | 2015-06-05 | 2015-09-16 | 华南理工大学 | Emulsion-type polyacrylate pressure-sensitive adhesive, and preparation method and application thereof |
KR20160011683A (en) * | 2016-01-12 | 2016-02-01 | 주식회사 엘지화학 | Method of Producing Acrylic Emulsion Comprising Tackifier |
CN105623561A (en) * | 2016-03-25 | 2016-06-01 | 江南大学 | Paper flocking adhesive and preparation method thereof |
CN108084927A (en) * | 2016-11-19 | 2018-05-29 | 辽宁东夫材料科技有限公司 | A kind of water soluble acrylic acid adhesive and preparation method thereof |
CN108410398A (en) * | 2018-04-04 | 2018-08-17 | 常州五荣化工有限公司 | A kind of preparation method of emulsion acrylate contact adhesive |
Non-Patent Citations (2)
Title |
---|
李红强: "《胶粘原理、技术及应用》", 31 January 2014, 华南理工大学出版社 * |
潘杰: "《印品装饰工(上)》", 29 February 2016, 文化发展出版社 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111100522A (en) * | 2019-12-26 | 2020-05-05 | 万华化学集团股份有限公司 | Interior wall coating with lasting fragrance and preparation method thereof |
CN111187586A (en) * | 2020-01-21 | 2020-05-22 | 江苏景宏新材料科技有限公司 | Ultra-high viscosity acrylate emulsion pressure-sensitive adhesive and preparation method thereof |
CN111187586B (en) * | 2020-01-21 | 2021-07-20 | 江苏景宏新材料科技有限公司 | Ultra-high viscosity acrylate emulsion pressure-sensitive adhesive and preparation method thereof |
CN114958243A (en) * | 2022-06-30 | 2022-08-30 | 浙江冠豪新材料有限公司 | Pressure-sensitive adhesive label and preparation method thereof |
CN117903683A (en) * | 2024-01-17 | 2024-04-19 | 中山市鑫峰光固化材料有限公司 | Soft light water-based light-cured coating and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN109517544B (en) | 2021-06-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109517544A (en) | A kind of environment-friendly type aqueous preparation method for pasting box glue and the product obtained by this method | |
CN102140320B (en) | Water-based polyacrylic emulsion laminating adhesive and preparation method thereof | |
CN102134465B (en) | Self-crosslinking aqueous complex film adhesive and preparation method thereof | |
CN107083215B (en) | A kind of ceramic tile gum produced by pure acrylate elastic emulsion and styrene-acrylic emulsion and technique | |
CN101698783B (en) | Dry-type compound aqueous paper/plastic laminating emulsion adhesive and preparation method thereof | |
CN113621103B (en) | Amine-free elastic acrylate emulsion, waterproof coating and preparation method | |
CN102140318B (en) | Water-based aluminized transfer glue and preparation method thereof | |
CN101864258A (en) | Low temperature resistant seal adhesive and preparation method thereof | |
US6136903A (en) | Repulpable, pressure-sensitive adhesive compositions | |
CN102134463B (en) | Water-based dry-type complex film adhesive and preparation method thereof | |
US20240052215A1 (en) | Method for preparing acrylate laminating adhesive by soap-free emulsion polymerization | |
CN112724887A (en) | Water-based acrylate pressure-sensitive adhesive emulsion for low-surface-energy material protective film and preparation method thereof | |
CN110511388A (en) | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing | |
CN107936878A (en) | A kind of high viscous emulsion-type pressure-sensitive adhesive and preparation method thereof | |
CN109929067A (en) | A kind of core-shell structure acrylic acid ester emulsion and its preparation method and application | |
DE102005022166A1 (en) | Laminates, process for their preparation and use | |
CN102559104B (en) | Waterborne gravure printing aluminum-coated compound glue and preparation method thereof | |
CN106010380B (en) | A kind of method that pickering emulsion polymerizations prepare water-fast albefaction acrylic emulsion pressure sensitive adhesive | |
CN108659752B (en) | Water-soluble polyacrylate pressure-sensitive adhesive for labels, and preparation method and application thereof | |
CN109837046A (en) | A kind of compound aqueous adhesive and preparation method thereof of plastic film dry type | |
CN109321153A (en) | The ultralow viscous protective film water-borne pressure sensitive adhesive of one kind, ultralow viscous protective film and preparation method thereof | |
CN114573759A (en) | Self-crosslinking styrene-acrylic emulsion for producing waterproof wood strip lines and preparation method thereof | |
CN113583597A (en) | Preparation process of water-based sealing adhesive | |
JP2007224184A (en) | Acrylic polymer-containing composition emulsion and method for producing the same | |
CN110218536A (en) | A kind of aqueous paper/plastic laminating emulsion adhesive and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |