CN1038192C - Electrostatic flocking adhesives solidifying under normal temperature - Google Patents
Electrostatic flocking adhesives solidifying under normal temperature Download PDFInfo
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- CN1038192C CN1038192C CN94104553A CN94104553A CN1038192C CN 1038192 C CN1038192 C CN 1038192C CN 94104553 A CN94104553 A CN 94104553A CN 94104553 A CN94104553 A CN 94104553A CN 1038192 C CN1038192 C CN 1038192C
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Abstract
The present invention belongs to adhesive for resin electrostatic flocking, which is used for base materials, such as leather, rubber, plastics, fabrics, paper, metal, wood, cement, porcelain tiles, walls, etc. The present invention is characterized in that the adhesive can be solidified at normal temperature, and can be used for electrostatic flocking on various base materials. The flocking products have the characteristics of high bonding strength, good abrasive resistance, good water-washing resistant performance, good weatherproof performance and solvent resistance and no damage of structures and performance of base materials.
Description
The invention belongs to resin static flocking bonding agent and application thereof.
It is with vinyl unsaturated monomers such as esters of acrylic acids, in the presence of water-fast Resins, epoxy, add under the condition of acrylate or vinylformic acid and N hydroxymethyl acrylamide, adopt first emulsification, the emulsification dripping method technology that the back drips continuously, and whole technology need not be led to rare gas element.Under nitrogen protection, the flocking adhesive made from letex polymerization of solidified at normal temperatures.This tackiness agent is used for carrying out static flocking on the various base materials such as leather, rubber, plastics, fabric, paper, metal, timber, cement, ceramic tile and body of wall, and can be in ambient cure.Flock printed article has the bonding strength height, wear resistance is good, water resistance is good, weather-proof and characteristics that solvent resistance is good.
Flocking adhesive used acrylic ester monomer usually in the past, added linking agent, synthesized with emulsion polymerisation process.But this flocking adhesive can only solidify under hot conditions or be crosslinked, general solidification value must be more than 130 ℃, this has just limited the use range of tackiness agent greatly, simultaneously because hot setting just may play destruction to the structure and the performance of static flocking base material.For example carry out flocking with sheepskin as base material, be cured crosslinkedly being higher than 90 ℃ of temperature, then can damage the structure of sheepskin, make the protein structure sex change in the sheepskin, the leather hardening, become fragile, the leather shrinking percentage is big simultaneously.On the base materials such as this external cement, ceramic tile, body of wall, the solidified flocking adhesive then can't use under the hot conditions.
Usually adopted the method for continuous dripping method or emulsion seeding polymerization to synthesize copolymer emulsion with vinyl unsaturated monomer letex polymerizations such as esters of acrylic acids in the past.But in the method reaction times of emulsion seeding polymerization long (more than 10 hours), plant factor is low, and throughput is little.When in esters of acrylic acid-epoxy-resin systems, adopting the continuous dripping method of monomer, in polymerization process, easily produce coacervation, and vinyl unsaturated monomers such as Resins, epoxy and esters of acrylic acid are difficult for mixing.
The method that drips continuously after the present invention adopts esters of acrylic acid-epoxy-resin systems with first emulsification can overcome above-mentioned shortcoming.Because contain Resins, epoxy in the copolymer emulsion, it has force of cohesion height, strong, the good water resistance excellence of solvent resistance of bonding force, the speciality of available multiple solidifying agent ambient cure; Owing to the polymerization process of continuous dripping method after the first emulsification of employing, system mixes, and forms uniform milk sap simultaneously, is difficult for layering and produces coacervation, can obtain the copolymer emulsion of steady quality, good reproducibility.
Characteristics of the present invention are:
1. flocking adhesive, its major ingredient is the interpenetrating(polymer)networks copolymer emulsion that contains esters of acrylic acid, epoxy resin, vinylformic acid or vinylformic acid and amides, adds ambient cure agent and thickening material again.
2. this flock binder is characterized in that acrylic ester monomer content is that 50-90 part (weight), epoxy resin content are that 5-50 part (weight), vinylformic acid or vinylformic acid and amides content are 1-10 part (weight).
3. flock binder of the present invention is characterized in that acrylic ester monomer can be methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, methyl methacrylate etc.Its consumption is 50-90 part (weight), especially with 60-80 part (weight) for well.
4. acrylic ester monomer of the present invention, it is characterized in that one or both or multiple acrylic ester monomer mix use, the ratio between each monomer is as the criterion to satisfy performances such as copolymer emulsion film-forming properties, viscosity, hardness, tensile strength, elongation, water-absorbent.
5. flock binder of the present invention is characterized in that Resins, epoxy can use cycloaliphatic epoxy resin, aromatic epoxy resin, aliphatic epoxy resin; Usually adopt bisphenol A type epoxy resin, as E-51, E-44, E-42, E-33, E-31 etc.Its consumption is 5-50 part (weight), especially with 10-30 part (weight) for well.Its content is low, and then adhesiveproperties is poor, too high levels, and then shrinking percentage height, fragility are big.
6. flock binder of the present invention is characterized in that acid amides can be the unsaturated aliphatic acid amides; The most handy N hydroxymethyl acrylamide.
7. one kind prepares the method for interpenetrating(polymer)networks copolymer emulsion with emulsion polymerisation process, it is characterized in that adopting first emulsification, the emulsification dripping method technology that the back drips continuously.
8. the method for making of flock binder of the present invention is characterized in that adopting anionic emulsifier and nonionic emulsifier blended emulsifying agent; Water-soluble cpds such as Potassium Persulphate or ammonium persulphate is as initiator.
9. one kind prepares the method for interpenetrating(polymer)networks copolymer emulsion with emulsion polymerisation process, it is characterized in that the polymerization temperature that adopts is 50-90 ℃, is preferably 75-85 ℃.
10. one kind prepares the method for interpenetrating(polymer)networks copolymer emulsion with emulsion polymerisation process, it is characterized in that adopting auxiliary agents such as adding ionogen, buffer reagent, softening agent, fire retardant, oxidation inhibitor, frostproofer, pigment.
11. flock binder of the present invention is characterized in that tackiness agent can ambient cure.
12. flock binder of the present invention is characterized in that this tackiness agent is used for base materials such as leather, rubber, plastics, fabric, paper, metal, timber, cement, ceramic tile and body of wall.
Vinylformic acid used in the present invention, methacrylic acid and N hydroxymethyl acrylamide etc. have the monomer of reactive functional groups, and its purpose is to improve the mechanical stability of polymerization system and increases state of cure.Its consumption in 1-10 part (weight) scope, especially in 6-10 part (weight) (with 100 parts of monomer weights) for well.Add-on is too small, and the emulsion mechanical stability descends, and state of cure is low when solidifying; Add-on is too high, and then polymerization system is acid strong, and stability of emulsion also descends.
Emulsifying agent used in the present invention is that anionic emulsifier and nonionic emulsifier mix use.Nonionic emulsifier has Triton X-100 emulsifying agent etc., as emulsifier op-10, OP-20, OP-100; Anionic emulsifier is Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, dodecyl phenenyl sulfate, and its consumption, anionic emulsifier are the 0.5-3% of acrylic ester monomer gross weight; Nonionic emulsifier is the 2%-6% of acrylic ester monomer gross weight; Consumption is too much, and then latex particle is more, and speed of response is fast, and molecular weight is big, and easily produces frothing in polymerization process; Consumption is few, and then latex particle is few, and speed of response is slow, long reaction time, and molecular weight is low.
Initiator used in the present invention is water-soluble cpdss such as Potassium Persulphate or ammonium persulphate.Its consumption is the 0.1%-1% of acrylic ester monomer gross weight; Especially with 0.2%-0.6% for well.Initiator amount is few, and speed of response is slow, long reaction time, molecular weight height; Initiator amount is many, and speed of response is fast, and molecular weight is low.
Polymeric reaction temperature of the present invention is 50-90 ℃, is preferably 75-85 ℃.Polymeric reaction temperature is lower than 50 ℃, and then decomposition of initiator becomes the speed of free radical low, and speed of response is slow, long reaction time; Polymeric reaction temperature is higher than 90 ℃, and it is fast that then decomposition of initiator becomes the speed of free radical, and speed of response is fast, but polymerization exotherm is big, easily produces coacervation or implode.
For satisfying the requirement of binder performance, increase the stability of copolymer emulsion, can suitably add auxiliary agents such as small amount of electrolyte, buffer reagent, softening agent, fire retardant, oxidation inhibitor, frostproofer, pigment as required.They can add respectively at the different time of reaction, are useful to improving polymer properties and satisfying service requirements.
The present invention is owing to use esters of acrylic acid-vinylformic acid-epoxy-resin systems, adopt first emulsification, the polymerization technique of the emulsification dripping method that the back drips continuously, make solidified flocking adhesive emulsion at normal temperatures, be characterized under the normal temperature solidifying, can on multiple base material, carry out static flocking, and flock printed article has the bonding strength height, wear resistance is good, wash durability is good, Nai Hou and solvent resistance are good, do not damage the characteristics of matrix structure and performance, thereby finished the present invention.
With executing example the present invention is described below:
Embodiment 1
(1). with following component
Methyl acrylate 120g
Butyl acrylate 250g
Methyl methacrylate 100g
Vinylformic acid 30g
Resins, epoxy (E44 of Wuxi resin processing plant) 100g
Place 1000 milliliters of glass beakers, mix, compositing monomer mixed solution (A);
(2). with following component
Deionized water 400g
Sodium dodecylbenzene sulfonate 8g
Emulsifier op-10 20g
Place 2000 milliliters of glass beakers, under optimal temperature, mix, form emulsifier aqueous solution (B);
(3). under high-speed stirring, (A) component evenly is added drop-wise in (B) component removes compositing monomer milk sap (C);
(4). agitator is being housed, condenser, in 2000 milliliters of four-hole reactors of dropping funnel and thermometer, add 10% above-mentioned (C), under agitation, make reactor temperature be raised to 70 ℃, adding concentration with dropping funnel is 40 parts of 2% (weight) persulfate aqueous solutions, because heat of polymerization, temperature of reaction is raised to 80 ℃ gradually, then under uniform temp, the monomer milk sap (C) and the concentration that dripped residue 90% with 2 hours are 160 parts of 2% (weight) persulfate aqueous solutions, carry out polyreaction, after dropwising, be incubated 1-3 hour again, cool to room temperature is that 25% (weight) ammonia soln adjusting pH value is 7-8 with concentration subsequently, obtains copolymer emulsion of the present invention, its solid content is 50 ± 2% (weight), and viscosity is 150 centipoises (25 ℃).
(5). above-mentioned copolymer emulsion is pressed following prescription:
Emulsion: self-vulcanizing agent: thickening material=100: 1.5: (1-3) (weight) is mixed with tackiness agent, is coated on the sheepskin, carries out static flocking, and its electrostatic flocking technology is:
＜1 〉. fine hair: 3dm * 0.8mm nylon fiber
＜2 〉. coating method: brush
＜3 〉. static flocking voltage: 60-70kv
＜4 〉. distance between plates: 10 centimetres
Behind the static flocking, (25 ℃) solidified 48 hours at normal temperatures.Static flocking goods wear resistance and water resistance after the curing are:
Wear resistance (with reference to the FZ/T01011-91 method)
Dry grinding: 〉=10000 times
Wet-milling: 〉=2000 times
The anti-performance of soaping (with reference to GB3921-83)
60 ℃, 30 minutes, colour-fast, do not fall hair.Embodiment 2
(1). with following component
Methyl acrylate 120g
Butyl acrylate 260g
Methyl methacrylate 100g
Vinylformic acid 20g
Resins, epoxy (with embodiment 1) 150g
Place 1000 milliliters of glass beakers, mix under the room temperature, compositing monomer mixed solution (A);
(2). with following component
Deionized water 400g
Sodium lauryl sulphate 8g
Emulsifier op-10 20g
N hydroxymethyl acrylamide 20g
Place 2000 milliliters of glass beakers, at room temperature mix, form the aqueous solution (B) of emulsifying agent, partial monosomy;
(3). use the method identical with embodiment (1) to make copolymer emulsion (C), content is 50 ± 2% (weight), and viscosity is 180 centipoises (25 ℃);
(4). above-mentioned copolymer emulsion is pressed following compositing formula:
Emulsion: self-vulcanizing agent: thickening material=100: 1.5: (1-3) (weight) is mixed with tackiness agent, be coated on the materials such as cement, paper, igelite, timber, body of wall and aluminium sheet, carry out static flocking, behind the static flocking, (25 ℃) solidified 48 hours at normal temperatures.Static flocking goods bonding strength height after the curing steeps or flushing with cold water or 60 ℃ of water loggings, and is colour-fast, do not fall hair.Abrasion resistance 〉=10000 time.
Embodiment 3
(1). with following component
Methyl acrylate 60g
Butyl acrylate 200g
Methyl methacrylate 100g
Vinylformic acid 40g
Resins, epoxy (with embodiment 1) 150g
2-EHA 100g
Place 1000 milliliters of glass beakers, at room temperature mix, compositing monomer mixed solution (A);
(2). with following component
Deionized water 420g
Sodium lauryl sulphate 10g
Emulsifier op-10 15g
Place 2000 milliliters of glass beakers, at room temperature mix, form the emulsifying agent body aqueous solution (B);
(3). use the method identical with embodiment (1) to make copolymer emulsion (C), its solid content content is 50.8 ± 2% (weight), and viscosity is 160 centipoises (25 ℃);
(4). above-mentioned copolymer emulsion is pressed following compositing formula:
Emulsion: self-vulcanizing agent: thickening material=100: 1.5: (1-3) (weight) is mixed with tackiness agent, be coated on 20 * 20 square centimeters the material such as rubber plate, three-ply-wood, white ceramic tile, fiberboard, fabric, it is carried out static flocking, and (25 ℃) solidified 48 hours at normal temperatures.Static flocking goods wear resistance after the curing is:
Dry grinding: 〉=10000 times
Wet-milling: 〉=2000 times
In 60 ℃ of water, soak half an hour, colour-fast, do not fall hair.
Comparative example 1:
(1). do not add Resins, epoxy in monomer, all the other are used and the identical component of embodiment (1), technology, make copolymer emulsion;
(2). above-mentioned copolymer emulsion is pressed following compositing formula:
Emulsion: self-vulcanizing agent: thickening material=100: 5: (1-3) (weight) is mixed with tackiness agent, is coated on the sheepskin material, and it is carried out static flocking, subsequently:
＜1 〉. solidified 0.5 hour at 140 ℃.Static flocking goods wear resistance after the curing is:
Dry grinding: 〉=10000 times
Wet-milling: 〉=2000 times
Sheepskin shrinks: 10%
Feel: harden, embrittlement
Steep half an hour 60 ℃ of water loggings, colour-fast, do not fall hair.
＜2 〉. (25 ℃) solidified 48 hours at normal temperatures.Static flocking goods after the curing steep half an hour 60 ℃ of water loggings, and tackiness agent separates with sheepskin.
Comparative example 2:
(1). do not add Resins, epoxy in monomer, all the other are used with the identical component of embodiment (2), technology and make copolymer emulsion;
(2), above-mentioned copolymer emulsion is pressed following compositing formula:
Emulsion: solidifying agent: thickening material=100: 5: (1-3) (weight) is mixed with tackiness agent, is coated on the cement material, and it is carried out static flocking, and (25 ℃) solidified 48 hours at normal temperatures.The water flushing subsequently of static flocking goods after the curing, villus shedding.
Claims (5)
1. electrostatic flocking adhesives solidifying under normal temperature, its composition contains the mixture copolymer emulsion of esters of acrylic acid-epoxy resin-vinylformic acid or vinylformic acid and amides and thickening material, ambient cure agent, it is characterized in that in the copolymer emulsion, each components in proportions is: acrylic ester monomer content is that 50-90 part (weight), epoxy resin content are that the content of the mixture of 5-50 part (weight), vinylformic acid or vinylformic acid and amides is 1-10 part (weight), and wherein the weight ratio of vinylformic acid and amides is 1: 1; Acrylic ester monomer can be methyl acrylate, ethyl propenoate, 2-EHA or methyl methacrylate; Resins, epoxy can be cycloaliphatic epoxy resin, aromatic epoxy resin or aliphatic epoxy resin; Amides is the unsaturated aliphatic acid amides; Its copolymer emulsion is the interpenetrating(polymer)networks copolymer emulsions, the emulsification dripping method prepared that adopts first emulsification, back to drip continuously, emulsifying agent adopts anionic emulsifier and nonionic emulsifier blending emulsifiers, and the two usage ratio is counted 0.5%-3% with the acrylic ester monomer gross weight: 2%-6%; Catalyzer adopts water miscible Potassium Persulphate or ammonium persulphate; Co-polymerization temperature is 50-90 ℃.
2. electrostatic flocking adhesives solidifying under normal temperature according to claim 1 is characterized in that aromatic epoxy resin adopts bisphenol A type epoxy resin E-51, E-44, E-42, E-33 or E-31.
3. electrostatic flocking adhesives solidifying under normal temperature according to claim 1 is characterized in that the unsaturated aliphatic acid amides is a N hydroxymethyl acrylamide.
4. electrostatic flocking adhesives solidifying under normal temperature according to claim 1 is characterized in that polymerization temperature is 75-85 ℃.
5. the application of the described ambient cure flocking adhesive of claim 1 is characterized in that this tackiness agent is used for the matrix of leather, rubber, plastics, fabric, paper, metal, timber, cement, ceramic tile or body of wall.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104553A CN1038192C (en) | 1994-05-03 | 1994-05-03 | Electrostatic flocking adhesives solidifying under normal temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104553A CN1038192C (en) | 1994-05-03 | 1994-05-03 | Electrostatic flocking adhesives solidifying under normal temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1122355A CN1122355A (en) | 1996-05-15 |
| CN1038192C true CN1038192C (en) | 1998-04-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104553A Expired - Fee Related CN1038192C (en) | 1994-05-03 | 1994-05-03 | Electrostatic flocking adhesives solidifying under normal temperature |
Country Status (1)
| Country | Link |
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| CN (1) | CN1038192C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008004112A1 (en) * | 2008-01-11 | 2009-07-16 | Saertex Gmbh & Co. Kg | Semifinished textile product with at least one surface provided with an adhesive |
| CN102659976A (en) * | 2012-04-16 | 2012-09-12 | 上海中新裕祥化工有限公司 | Novel aqueous light-cured alicyclic epoxy acrylic acid emulsion and preparation method thereof |
| CN102675530A (en) * | 2012-04-23 | 2012-09-19 | 上海中新裕祥化工有限公司 | Novel aqueous acrylic acid modified alicyclic epoxy emulsion and preparation method thereof |
| CN103214993B (en) * | 2013-05-04 | 2015-01-28 | 辽宁恒星精细化工有限公司 | Acrylic ester electrostatic flocking binding agent and preparation method thereof |
| CN103525345B (en) * | 2013-10-10 | 2016-03-30 | 杨毅 | Flock Adhesive stick |
| CN105315413A (en) * | 2015-11-24 | 2016-02-10 | 太仓市金锚新材料科技有限公司 | Novel modified acrylate emulsion adhesive and preparation method thereof |
| CN105441013B (en) * | 2015-11-26 | 2017-12-26 | 河南豫冠化工科技开发有限公司 | The preparation technology of water proof and wearable two-component resin adhesive |
| CN109853103A (en) * | 2019-02-26 | 2019-06-07 | 浙江久大纺织科技有限公司 | A kind of preparation method of antistatic flocking yarn |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03177480A (en) * | 1989-12-06 | 1991-08-01 | Mitsui Toatsu Chem Inc | Two-pack type acrylic emulsion-based adhesive |
| JPH03177479A (en) * | 1989-12-05 | 1991-08-01 | Mitsui Toatsu Chem Inc | Adhesive for electrostatic hair setting |
| CN1085931A (en) * | 1992-10-19 | 1994-04-27 | 化学工业部天津化工研究院 | The rubber static flocking production method of binding agent |
-
1994
- 1994-05-03 CN CN94104553A patent/CN1038192C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03177479A (en) * | 1989-12-05 | 1991-08-01 | Mitsui Toatsu Chem Inc | Adhesive for electrostatic hair setting |
| JPH03177480A (en) * | 1989-12-06 | 1991-08-01 | Mitsui Toatsu Chem Inc | Two-pack type acrylic emulsion-based adhesive |
| CN1085931A (en) * | 1992-10-19 | 1994-04-27 | 化学工业部天津化工研究院 | The rubber static flocking production method of binding agent |
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| Publication number | Publication date |
|---|---|
| CN1122355A (en) | 1996-05-15 |
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