CN101412783A - Preparation of acrylic ester copolymer emulsion for pressure-sensitive adhesive - Google Patents
Preparation of acrylic ester copolymer emulsion for pressure-sensitive adhesive Download PDFInfo
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- CN101412783A CN101412783A CNA2008101535499A CN200810153549A CN101412783A CN 101412783 A CN101412783 A CN 101412783A CN A2008101535499 A CNA2008101535499 A CN A2008101535499A CN 200810153549 A CN200810153549 A CN 200810153549A CN 101412783 A CN101412783 A CN 101412783A
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Abstract
The invention relates to a method for preparing an acrylate polymer emulsion used for a pressure sensitive adhesive, which belongs to an adhesive based on acrylate polymer. The method for preparing the acrylate polymer emulsion used for the pressure sensitive adhesive comprises the following steps: (1) preparation of a seed emulsion; (2) pre-emulsification of shell layer monomers; and (3) gradient feeding of a shell layer. The method adopts the seed emulsion polymerization technology to drip a hard monomer, namely methyl methacrylate (MMA) into the shell layer, so that the concentration is subjected to discontinuous change and the organic-inorganic acrylate polymer emulsion provided with an obvious core-shell structure is prepared, wherein nano silicon dioxide is taken as a core and a copolymer of acrylic ester and acrylic monomers is taken as the shell layer; and the hard monomer of the shell layer is subjected to concentration gradient change. The acrylate polymer emulsion can be used as the pressure sensitive adhesive after drying and film forming; the prepared pressure sensitive adhesive has the advantages of high continuous viscous force and reduction of the residual gum content under the condition of gum peeling; and the initial adhesion and the peeling strength can be improved when the continuous viscous force is larger.
Description
Technical field
Technical scheme of the present invention relates to the tackiness agent based on acrylate copolymer, specifically a kind of preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive.
Background technology
Pressure-sensitive adhesive can be by prepared such as letex polymerization, solution polymerization, heating and melting and ultraviolet light polymerizations.But, in recent years, the continuous expansion of environmental protection, safety, energy-conservation etc. attention and pressure sensitive adhesive being used along with people, impel pressure sensitive adhesive to develop towards low pollution, province's energy, high-performance and multifunction direction, particularly developed country proposes after nuisanceless, pollution-free, resource-saving, the prerequisite of province's energy as the development adhesives industries, water-base emulsion type pressure-sensitive adhesive causes the great interest of people, especially acrylate copolymer emulsion type pressure-sensitive adhesive.Because it has characteristics such as good weathering resistance, alkali resistance, scale resistance, ozone resistance, photostabilization and stink are few, has promoted the develop rapidly of acrylate copolymer emulsion polymeric.After direct oxidation of propylene prepared the technology invention of acrylic acid series product, the price of acrylate monomer descended significantly.Now, acrylate pressure-sensitive adhesive has surpassed the natural rubber pressure sensitive adhesive, becomes the kind of output maximum in the pressure-sensitive adhesive.
Coventional type emulsion acrylic ester pressure-sensitive mostly is polymkeric substance-polymer-type on the market, and there is following shortcoming in this kind glue: the initial cohesiveness of pressure sensitive adhesive, when stripping performance is good, and holding viscosity can variation; Hold viscosity can be good the time, initial cohesiveness and stripping performance will variation, can not realize initial cohesiveness, stripping performance simultaneously and hold viscosity balance [M.D.Gower preferably, R.A.Shanks.The effect of varied monomer composition on adhesive performance and peeling mastercures for acrylic pressure-sensitive adhesives.Journal of Applied Polymer Science, 2004, Vol.93,2909-2917].In recent years, organic-inorganic nanocomposite causes that people pay much attention to, because nano material is used for polymkeric substance, can improve mechanics, calorifics, electricity, optics and the processing characteristics of macromolecular material, improve toughness, intensity, thermotolerance and the flame retardant resistance etc. of polymkeric substance.And in the application of pressure sensitive adhesive, can all be improved aspect voltage-dependent characteristic and the water tolerance owing to contain the pressure-sensitive adhesive emulsion of nanoparticle, so the present invention is incorporated into the stratum nucleare of acrylate copolymer emulsion with silicon-dioxide and adopts in the pressure sensitive adhesive preparation of gradient feed way at shell.
Usually silicon-dioxide exists with two kinds of forms, and a kind of is powder silicon-dioxide, and another kind is a colloidal sol silicon-dioxide.Powder silicon-dioxide is because its specific surface area is big, specific surface energy is high, is difficult to carry out with single particle form and polymkeric substance compound, and its surface needs finishing to realize compound with polymkeric substance to reduce its surface energy; Colloid silica can adopt sol-gel method and the preparation of water glass hydrolysis method again, but the silicon dioxide gel solid content of sol-gel method preparation is low, and cost is higher, complex process, and present this technology realizes that industrialized possibility is less; And pass through the silica hydrosol that the water glass hydrolysis method prepares, because the starting raw material water glass is easy to get, preparation process technology is simple, has realized suitability for industrialized production at present, and is with low cost; The most important thing is that it can disperse with nano level in the aqueous solution.Therefore, the silica hydrosol first-selection can be prepared organic and inorganic acrylate copolymer emulsion type pressure sensitive adhesive.
Polymer gradient-structure copolymer material is meant the increase along with latex particle size of chemical constitution or microtexture, and occupying an leading position from a kind of monomer changes to the prevailing multipolymer of another kind of monomer.The material of this structure begun to be widely used at medical material, separatory membrane, coating, caking agent and noise reduction sound absorption damping material field [Sun Wenbing. the preparation research of polymer gradient material. material Leader, 2006,20 (7): 95-98].People such as Aymonier are main raw material with methyl methacrylate (MMA) with Isooctyl acrylate monomer (2-EHA), drip comonomer respectively by semicontinuous gradient emulsion polymerisation process and enter reaction system, make monomer and form uneven emulsion particle and film thereof, but this film is because soft, the shortage of hard phase region consistency causes bonding and the cohesive fracture, show inharmonic viscoelastic behavior, promptly mainly show as elastic behavior (low wettability) in adhesion process, and mainly showing as viscous fluid behavior (poly-failure in low-energy) in the debinding process, the pressure-sensitive character that is obtained is relatively poor.[1Aymonier A, Leclercq D, Tordjeman P, et al.Journal of Applied Polymer Science, 2003,89:2749-2756; 2 Wu Hui, Gong Jun, Li Jianzong. the structure activity relationship of polyalcohol emulsion particle form, membrane structure and pressure-sensitive character. polymer material science and engineering, 2008,24 (5): 108-111].
Two patents (CN1944479A and CN1944480A) of the previous application of the present inventor also are silicon-dioxide and acrylate to be carried out in-situ polymerization make acrylate pressure-sensitive adhesive.But owing to introduce evenly adding of methyl methacrylate (MMA) in the hard monomer process by shell, easily on adherend, stay cull after thereby the emulsion acrylate pressure sensitive adhesive that the emulsion particle that makes makes existence is peeled off, when initial bonding strength is big, hold shortcomings such as viscous force can reduce.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive is provided, and it is the discrete steps and changes that to make with the nano silicon be that the multipolymer of nuclear, acrylate and Acrylic Acid Monomer is inorganic-organic acrylate copolymer emulsion with obvious nucleocapsid structure that shell and shell hard monomer are the concentration gradient variation by drip hard monomer methyl methacrylate (MMA) concentration to shell with the seeded emulsion polymerization technology.To promptly get the acrylate copolymer pressure-sensitive adhesive after this emulsion film drying.Not only can improve with the gradient feed way and to hold viscous force, but also can make gained inorganic-organic core-shell emulsion type acrylate copolymer pressure sensitive adhesive peels off the residual silkgum content that the back stays and reduces to zero on adherend; When initial bonding strength increases, peeling force, hold viscous force and also can keep higher value.
Technical scheme of the present invention is:
A kind of preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive may further comprise the steps:
1. the preparation of seed emulsion: in the time of 83 ℃, in aggregation container, after being to add the nano silicon water-sol in 0.10%～0.14% the emulsifier aqueous solution, stirred 10 minutes mass percent concentration, add the initiator mass percent concentration again and be 1.64% potassium persulfate solution, be incubated 15～25 minutes then; Its mass ratio is an emulsifier solution: silica hydrosol: potassium persulfate solution=200～202:4.96:36.6;
2. pre-emulsification of shell monomer: the methyl methacrylate of shell monomers quality n * m * 3.6% is divided into 6 parts, adds other (methyl) vinylformic acid and esters monomers thereof again, make to form the shell monomers that 6 parts of quality equate; Emulsifying agent, chain-transfer agent uncle lauryl mercaptan are divided into 6 equal portions after mixing, and it is mixed with top 6 parts of corresponding shell monomers respectively, form pre-emulsion at last, wherein the quality proportioning of used material is an emulsifying agent: shell monomers: uncle's lauryl mercaptan=1.5～1.8:120:0.04;
Top m=1 or 2, the value of n is one of following dual mode: first kind: n=0,1,2,3,4,5 (it is positive gradient that the quality of methyl methacrylate increases gradually); Perhaps second kind: n=5,4,3,2,1,0 (it is antigradient that the quality of methyl methacrylate reduces gradually);
Above described other (methyl) vinylformic acid and esters monomer thereof be 2～3 kinds mixture in vinylformic acid, butyl acrylate and the 2-EHA, wherein must contain vinylformic acid;
Step 1. and the emulsifying agent 2. be succinate sodium 2-ethylhexyl, fatty alcohol-polyoxyethylene ether or its mixture.
3. shell-grade charging: in the time of 83 ℃, 6 parts of pre-emulsions of last step preparation are dripped in the seed emulsion that step makes in 1. successively by the every interval of the value order of top n 30 minutes, total dropping time is 3 hours, every interval added again in one hour mass percent concentration be 0.443% persulfate aqueous solution once, wherein mass ratio is every part of shell pre-emulsion: seed emulsion: persulfate aqueous solution total amount=18～25:240～244:36.15, be incubated 1 hour more afterwards, reduce to 40 ℃ of dischargings, promptly get the silicon dioxide-acrylate copolymer emulsion.
The preparation method of a kind of acrylic ester copolymer emulsion for pressure-sensitive adhesive recited above, the nano silicon water-sol of step described in 1. be commercially available silica hydrosol product or use as polishing fluid after silica hydrosol after filtering through 300 eye mesh screens, its solid content is 42%～45%, and particle diameter is between 40～95nm.
The preparation method of a kind of acrylic ester copolymer emulsion for pressure-sensitive adhesive recited above, step 2. described in every part of shell monomers acrylic acid content be that mass ratio is a vinylformic acid: every part of shell monomers=3:120.
This silicon dioxide-acrylate copolymer emulsion promptly can be used as pressure-sensitive adhesive and uses after the oven dry film forming.
180 ° of peeling forces, initial bonding strengths of pressure sensitive adhesive and hold sticking intensity respectively according to Britain FINAT Testing Methods No.1,8,9 standard tests (seeing for details in the embodiment).
The preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive of the present invention is with behind the nano silicon water-sol and the terminal electronegative acrylic ester polymer electrostatic attraction of macromole of gradient feeding manner with positively charged under the acidic conditions, adopts the seeded emulsion polymerization technology to make the inorganic-organic nucleocapsid structure pressure-sensitive adhesive silicon dioxide-acrylate copolymer emulsion with gradient-structure.Not only can make acrylate monomer carry out in-situ polymerization and make emulsion, and have better voltage-dependent characteristic with gradient-structure at the silica hydrosol skin.No agglomerated thing produces in this polymerization process, and the pressure sensitive adhesive characteristic experimental result shows: by changing the optimization that reinforced composition and mode have realized pressure sensitive adhesive characteristic, for example improve and hold viscous force; Residual silkgum content when minimizing glue is peeled off; Hold under the bigger situation of viscous force, improve initial bonding strength, peeling force etc.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
The size distribution figure of silicon-dioxide-acrylate copolymer latex among Fig. 1 embodiment 1.
The transmission electron microscope picture of silicon-dioxide-acrylate copolymer latex among Fig. 2 embodiment 1.
The 20min of Fig. 3 embodiment 4,5,6 pressure sensitive adhesive samples peels off and tries hard to (a: embodiment 4; B: embodiment 5; C: embodiment 6)
Embodiment
Those skilled in the art can be understood the present invention by following examples, but these embodiment do not limit the present invention.
Embodiment 1
The preparation of silicon dioxide-acrylate copolymer emulsion comprises following step:
1. the preparation of seed emulsion: in the time of 83 ℃, in aggregation container, 0.23g emulsifying agent succinate sodium 2-ethylhexyl is evenly added 4.96g silica hydrosol stirring 10 minutes in the back with the 200g water dissolution, adding the 36.6g mass ratio again is 1.64% initiator potassium persulfate solution, is incubated 15～25 minutes then; The nano silicon of this emulsion is a silica hydrosol, its can be commercially available silica hydrosol product or use as polishing fluid after silica hydrosol after filtering through 300 eye mesh screens, its solid content is 42%～45%, and particle diameter is between 40～95nm.
2. pre-emulsification of shell monomer: with the 10.8g methyl methacrylate according to n * 0.72g, n 0,1,2,3,4,5 is divided into 6 parts, adds 0.5g vinylformic acid in every part, the 106.2g butyl acrylate is added wherein again, form 6 parts of shell monomers, every part of shell monomers quality is 20g; Be divided into 6 equal portions after again 1.6g emulsifying agent succinate sodium 2-ethylhexyl and uncle's 0.04g lauryl mercaptan being mixed, and it is mixed the formation pre-emulsion with top 6 parts of corresponding shell monomers respectively; To increase gradually be positive gradient to the quality of methyl methacrylate in every part of pre-emulsion, and the MMA quality is as shown in table 1 over time during embodiment 1 gradient charging.
3. shell-grade charging: in the time of 83 ℃, 6 parts of pre-emulsions (every part of 20.27g) of preparation of last step are pressed top n=0,1,2,3,4,5 put in order every intervals 30 minutes drip fully in the 241.79g seed emulsion that step makes in 1. successively, total dropping time is 3 hours, the 12.05g persulfate aqueous solution was added once in one hour again in every therebetween interval, add altogether three times, this persulfate aqueous solution is dissolved in the 35.99g deionized water by the 0.16g Potassium Persulphate and makes, be incubated 1 hour more afterwards, reduce to 40 ℃ of dischargings, promptly get the silicon dioxide-acrylate copolymer emulsion.
Table 1 step is gradient charging MMA quality and the reinforced time relation of shell 2.
The latex particle size that records this emulsion with Malvern Zetasizer 3000HS microcosmic particle size analyzer is 246nm, and the size distribution index is 0.0213, as shown in Figure 1, illustrates that the latex particle of this emulsion is narrow discrete distribution, and size distribution is even.
With above-mentioned emulsion concentration is the pH value to 7.0 that 10% ammoniacal liquor is regulated emulsion, promptly get the silicon dioxide-acrylate copolymer emulsion after the thickening, again the emulsion after the thickening is coated on polyethylene terephthalate (PET) film substrate 105 ℃ down after dry 4 minutes, promptly gets the acrylate copolymer pressure-sensitive adhesive.
180 ° of peeling forces, initial bonding strengths of the acrylate copolymer pressure-sensitive adhesive that makes with the silicon dioxide-acrylate copolymer emulsion of the inventive method preparation and hold viscous force respectively according to Britain FINAT Testing Methods No.1,8,9 standard tests;
(1) peel test force: according to 180 ° of stripping strengths of Britain FINAT Testing Method No.1 standard test pressure-sensitive adhesive tape.Test board is a stainless steel plate, and length is 125mm ± 1mm, and width is 50mm ± 1mm, thickness 1.5～2.0mm.Before the test,, with clean absorbent gauze it is dried then, cleans so repeatedly three times with acetone and dehydrated alcohol washing test plate, until the working face of stainless steel plate till visual inspection reaches cleaning.It is long that adhesive tape one end that makes is peelled off 85mm, stick on the test board, and be that 84mm, width are that 45mm, quality are the slowly roll extrusion three times repeatedly on sample of rubber coating pressure roller of 2000g ± 50g with diameter, placed 20 minutes.With 180 ° of sample free end doublings, sample free end and test board are clipped in respectively on the last lower clamp of trier, and the release surface and the trier line of force are consistent, trier is peeled off with the speed of per minute 300mm, and draw and peel off curve, write down peeling force and maximum, force.180 ° of stripping strength σ of pressure-sensitive adhesive tape (kN/m) are calculated as follows:
S in the formula---the area in the recording curve in the span, mm
2
L---the length in the recording curve in the span, mm;
B---sealing tape developed width, mm;
C---the load of recording paper unit height, kN/m.
Each group sample number is no less than 3, and the test result of 180 ° of peel adhesion power is represented with the mean value of the peeling force (newton/25mm width) of 20 minutes or 3 battens recording under the time of repose in 24 hours.
(2) initial bonding strength test: according to the initial cohesiveness of Britain FINAT Testing Method No.8 standard test pressure-sensitive adhesive tape.This testing standard ring viscoelastic test method just of adopt hanging down promptly will be in contact with one another under special speed and pressure sensitive close ring that contact area is certain separates needed power with a certain standard surface.Select 3 wide 25mm ± 0.5mm that cut originally, the sample adhesive tape of length 200mm, the cut channel between the sample adhesive tape should be clean, straight.With the adhesive tape remove release paper, doubling is done circlewise, and its overlapping ends is fixed on the grip of testing machine upper end, and the lower end fixes a slick stainless steel plate, starts trier, and anchor clamps descend, and the ring that hangs down is fully contacted with stainless steel substrates.Anchor clamps are risen, test, record initial bonding strength and maximum, force.Testing tool: it is that the tensile testing machine of per minute 300mm and the size of surfacing are 25 ± 0.5mm * 80 ± 0.2mm stainless steel plate that vertical anchor clamps, velocity of separation are arranged.
(3) hold viscous force test: hold the viscosity energy according to Britain FINAT Testing Method No.9 standard test pressure-sensitive adhesive tape.By Britain FINAT Testing standard, it is on 2 ° the standard adherend sheet glass that sealing tape is sticked on the pitch angle with the area of long 25mm * wide 25mm, the weight that hangs up the 1000g quality at the sealing tape end of hanging makes and is subjected to force direction parallel fully with adhesive surface, and keep at a certain temperature, the slippage of record sealing tape is until the time t that comes off
0, promptly hold measuring of viscous force as the shear creep confining force of this sealing tape, because the quality of the size of the character of test result and adherend, stickup joint, weight and probe temperature etc. are relevant, so test condition must be consistent with testing standard.Wide adhesive tape one end of the 25mm that will prepare originally before the test is removed the interleaving paper of 25mm length, and promptly last bonding area is 25 * 25mm
2In bond length, can not contact hand or other object, with the remainder doubling, after the sealing, the part of removing interleaving paper is sticked on the sheet glass, the wheel of rubber rollers pressure device of using 2000 ± 50g then under deadweight approximately with the speed of per second 10mm to sample roll extrusion three times back and forth.
Fig. 2 is the transmission electron microscope picture of embodiment 1, does not reunite between particle as can be seen from figure, and the emulsion particle median size is 244nm, and size evenly.The parameter of made acrylic ester copolymer emulsion for pressure-sensitive adhesive sees Table 7 among the embodiment, and the performance of the acrylate copolymer pressure-sensitive adhesive that is made by these acrylate copolymer emulsions sees Table 8.
The preparation method:
1. the preparation of seed emulsion: with embodiment 1.
2. pre-emulsification of shell monomer: with the 10.8g methyl methacrylate according to n * 0.72g, n is that 5,4,3,2,1,0 (for embodiment 2) or n=2.5,2.5,2.5,2.5,2.5,2.5 (for embodiment 3) are divided into 6 parts, add 0.5g vinylformic acid in every part, again the 106.2g butyl acrylate is added wherein, form 6 parts of shell monomers, every part of shell monomers quality is 20g; Be divided into 6 equal portions after again 1.6g emulsifying agent succinate sodium 2-ethylhexyl and uncle's 0.04g lauryl mercaptan being mixed, and it is mixed the formation pre-emulsion with top 6 parts of corresponding shell monomers respectively; To reduce gradually be antigradient to the quality of methyl methacrylate in every part of pre-emulsion, and the constant mass of methyl methacrylate promptly evenly in every part of pre-emulsion.The MMA quality is as shown in table 2 over time during embodiment 2～3 gradient chargings.
3. shell-grade charging: in the time of 83 ℃, with 6 parts of pre-emulsions (every part of 20.27g) of last step preparation by top n be 5,4,3,2,1,0 or put in order every interval 30 minutes of n=2.5,2.5,2.5,2.5,2.5,2.5 in the 241.79g seed emulsion that step makes in 1., drip fully successively, all the other are with embodiment 1.
Table 2 step is gradient charging MMA quality and the reinforced time relation of shell 2.
The parameter of made acrylic ester copolymer emulsion for pressure-sensitive adhesive sees Table 7 in the foregoing description, and the performance of the acrylate copolymer pressure-sensitive adhesive that is made by these acrylate copolymer emulsions sees Table 8.
The preparation method:
1. the preparation of seed emulsion: with embodiment 1.
2. pre-emulsification of shell monomer: with the 21.6g methyl methacrylate according to n * 1.44g, n is that 0,1,2,3,4,5 (for embodiment 4) or n are that 5,4,3,2,1,0 (for embodiment 5) or n=2.5,2.5,2.5,2.5,2.5,2.5 (for embodiment 6) are divided into 6 parts, add 0.5g vinylformic acid in every part, again the 95.40g butyl acrylate is added wherein, form 6 parts of shell monomers, every part of shell monomers quality is 20g; Be divided into 6 equal portions after again 1.6g emulsifying agent succinate sodium 2-ethylhexyl and uncle's 0.04g lauryl mercaptan being mixed, and it is mixed the formation pre-emulsion with top 6 parts of corresponding shell monomers respectively.The MMA quality is as shown in table 3 over time during embodiment 4～6 gradient chargings.
3. shell-grade charging: in the time of 83 ℃, with 6 parts of pre-emulsions (every part of 20.27g) of last step preparation by top n be 0,1,2,3,4,5 or n be 5,4,3,2,1,0 or put in order every interval 30 minutes of n=2.5,2.5,2.5,2.5,2.5,2.5 in the 241.79g seed emulsion that step makes in 1., drip fully successively, all the other are with embodiment 1.
Table 3 step is gradient charging MMA content and the reinforced time relation of shell 2.
The parameter of made acrylic ester copolymer emulsion for pressure-sensitive adhesive sees Table 7 in the foregoing description, and the performance of the acrylate copolymer pressure-sensitive adhesive that is made by these acrylate copolymer emulsions sees Table 8.
Embodiment 7～9
The preparation method:
With the Isooctyl acrylate monomer of quality such as the Butyl Acrylate Monomer among the embodiment 1～3 all is changed to, all the other steps (preparation of seed emulsion, pre-emulsification of shell monomer, shell-grade charging) are with embodiment 1～3.The MMA quality is as shown in table 4 over time during embodiment 7～9 gradient chargings.
The reinforced time relation of MMA quality and shell during the charging of table 4 shell monomers pre-emulsion gradient
The parameter of made acrylic ester copolymer emulsion for pressure-sensitive adhesive sees Table 7 in the foregoing description, and the performance of the acrylate copolymer pressure-sensitive adhesive that is made by these acrylate copolymer emulsions sees Table 8.
The preparation method:
With the Isooctyl acrylate monomer of quality such as the Butyl Acrylate Monomer among the embodiment 4～6 all is changed to, all the other steps (preparation of seed emulsion, pre-emulsification of shell monomer, shell-grade charging) are with embodiment 4～6.The MMA quality is as shown in table 5 over time during embodiment 10～12 gradient chargings.
The reinforced time relation of MMA quality and shell during the charging of table 5 shell monomers pre-emulsion gradient
The parameter of made acrylic ester copolymer emulsion for pressure-sensitive adhesive sees Table 7 in the foregoing description, and the performance of the acrylate copolymer pressure-sensitive adhesive that is made by these acrylate copolymer emulsions sees Table 8.
Embodiment 13～15
The preparation method:
1. the preparation of seed emulsion: in the time of 83 ℃, in aggregation container, emulsifying agent (mixture of 0.2g succinate sodium 2-ethylhexyl and 0.05g fatty alcohol-polyoxyethylene ether) is evenly added 4.96g silica hydrosol stirring 10 minutes in the back with the 200g water dissolution, adding the 36.6g mass ratio again is 1.64% initiator potassium persulfate solution, is incubated 15～25 minutes then; The nano silicon of this emulsion is a silica hydrosol, its can be commercially available silica hydrosol product or use as polishing fluid after silica hydrosol after filtering through 300 eye mesh screens, its solid content is 42%～45%, and particle diameter is between 40～95nm.
2. pre-emulsification of shell monomer: with the 10.8g methyl methacrylate according to n * 0.72g, n=0,1,2,3,4,5 (for embodiment 13) or n are that 5,4,3,2,1,0 (for embodiment 14) or n=2.5,2.5,2.5,2.5,2.5,2.5 (for embodiment 15) are divided into 6 parts, add 0.5g vinylformic acid in every part, again the 106.2g Isooctyl acrylate monomer is added wherein, make to form 6 parts of shell monomers, every part of shell monomers quality is 20g; Be divided into 6 equal portions after again emulsifying agent (mixture of 1.44g succinate sodium 2-ethylhexyl and 0.36g fatty alcohol-polyoxyethylene ether) and uncle's 0.04g lauryl mercaptan being mixed, and it is mixed the formation pre-emulsion with top 6 parts of corresponding shell monomers respectively.The MMA quality is as shown in table 6 over time during embodiment 10～12 gradient chargings.
3. shell-grade charging: in the time of 83 ℃, 6 parts of pre-emulsions (every part of 20.31g) of preparation were 0 by top n with the last step, 1,2,3,4,5 or n be 5,4,3,2,1,0 or n=2.5,2.5,2.5,2.5,2.5, every interval 30 minutes drips fully in the 241.81g seed emulsion that step makes in 1. successively 2.5 put in order, total dropping time is 3 hours, the 12.05g persulfate aqueous solution was added once in one hour again in every therebetween interval, add altogether three times, this persulfate aqueous solution is dissolved in the 35.99g deionized water by the 0.16g Potassium Persulphate and makes, be incubated 1 hour more afterwards, reduce to 40 ℃ of dischargings, promptly get the silicon dioxide-acrylate copolymer emulsion.
Table 6 step is gradient charging MMA quality and the reinforced time relation of shell 2.
The parameter of made acrylic ester copolymer emulsion for pressure-sensitive adhesive sees Table 7 in the foregoing description, and the performance of the acrylate copolymer pressure-sensitive adhesive that is made by these acrylate copolymer emulsions sees Table 8.
The parameter table look-up of table 7 acrylic ester copolymer emulsion for pressure-sensitive adhesive
Annotate: % is with respect to all monomeric mass percents of shell in the table 7; Hold sticking strength test condition: 30 ℃ of probe temperatures, adherend are sheet glass, bond area 25mm * 25mm, weight quality 1000g; In the stripping performance, min representative minute, h representative hour.With even composition pressure sensitive adhesive is comparative example, under different methyl methacrylate content, investigates the improvement of gradient-structure to pressure sensitive adhesive characteristic.
All about 250nm, particle diameter is narrow discrete distribution to the latex particle particle diameter that is obtained by table 7, and solid content is about 30%, and transformation efficiency is all greater than 98%, and the pH value is about 2.5.
Institute's synthetic pressure sensitive adhesive characteristic table look-up among table 8 embodiment
The listed embodiment of above-mentioned table 8 can be divided into 5 groups and compare, and first group is example 1～3, and second group is example 4～6, and the 3rd group is example 7～9, and the 4th group is example 10～12, and the 5th group is example 13～15, and wherein embodiment 3,6, and 9,12,15 is comparative example.For institute's synthetic gradient-structure (positive gradient or antigradient) acrylate copolymer pressure sensitive adhesive, its initial bonding strength and peeling force and evenly the pressure sensitive adhesive characteristic that obtains of charging process (being comparative example) is suitable, and it is held sticking intensity and is greatly improved.In first group of embodiment, when consisting of the combination of methyl methacrylate and butyl acrylate,, hold sticking intensity and all improved more than 2 times no matter be positive gradient or antigradient concentration distribution.Under the Gradient distribution situation, the polymethylmethacrylate of high glass-transition temperature has improved the force of cohesion of acrylate copolymer significantly and has held sticking intensity owing to the increase of its partial concn.Second group of embodiment 4 shows, the gradient-structure pressure sensitive adhesive is under the situation that keeps initial bonding strength and peeling force, hold viscous force and not only improved more than 2 times, but also can make the cull area be reduced to zero, wherein the 20min of embodiment 4,5,6 pressure sensitive adhesives peels off and tries hard to see Fig. 3 (a: embodiment 4 wherein; B: embodiment 5; C: embodiment 6).The 3rd group of embodiment 8, the 4th group of embodiment 11 and the 5th group of embodiment 14 show, antigradient structure pressure sensitive adhesive not only has preferably initial bonding strength, peeling force but also its hold viscous force with respect to even composition pressure sensitive adhesive (being comparative example) increase is also arranged; The 3rd group of embodiment 7, the 4th group of embodiment 10 and the 5th group of embodiment 13 show, positive gradient structure pressure sensitive adhesive initial bonding strength, is held viscous force and can be increased to simultaneously and be about more than 2 times of corresponding even composition pressure sensitive adhesive (being comparative example) under peeling force descends few situation.Under the constant situation of raw material, can realize the optimization of pressure sensitive adhesive characteristic by changing component or feed way, residual silkgum content when for example reducing glue and peeling off, keeping initial bonding strength, peeling force to have under the situation of high value, hold sticking intensity and significantly improve, and hold normally contradiction of sticking intensity and initial bonding strength, peeling force value.
Claims (3)
1, a kind of preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive is characterized by and may further comprise the steps:
1. the preparation of seed emulsion: in the time of 83 ℃, in aggregation container, after being to add the nano silicon water-sol in 0.10%～0.14% the emulsifier aqueous solution, stirred 10 minutes mass percent concentration, add the initiator mass percent concentration again and be 1.64% potassium persulfate solution, be incubated 15～25 minutes then; Its mass ratio is an emulsifier solution: silica hydrosol: potassium persulfate solution=200～202:4.96:36.6;
2. pre-emulsification of shell monomer: the methyl methacrylate of shell monomers quality n * m * 3.6% is divided into 6 parts, adds other (methyl) vinylformic acid and esters monomers thereof again, make to form the shell monomers that 6 parts of quality equate; Emulsifying agent, chain-transfer agent uncle lauryl mercaptan are divided into 6 equal portions after mixing, and it is mixed with top 6 parts of corresponding shell monomers respectively, form pre-emulsion at last, wherein the quality proportioning of used material is an emulsifying agent: shell monomers: uncle's lauryl mercaptan=1.5～1.8:120:0.04;
Top m=1 or 2, the value of n is one of following dual mode: first kind, the quality of methyl methacrylate increases gradually: n=0,1,2,3,4,5; Perhaps second kind, the quality of methyl methacrylate reduces gradually: n=5,4,3,2,1,0;
Above described other (methyl) vinylformic acid and esters monomer thereof be 2～3 kinds mixture in vinylformic acid, butyl acrylate and the 2-EHA, wherein must contain vinylformic acid;
Step 1. and the emulsifying agent 2. be succinate sodium 2-ethylhexyl, fatty alcohol-polyoxyethylene ether or its mixture.
3. shell-grade charging: in the time of 83 ℃, 6 parts of pre-emulsions of last step preparation are dripped in the seed emulsion that step makes in 1. successively by the every interval of the value order of top n 30 minutes, total dropping time is 3 hours, every interval added again in one hour mass percent concentration be 0.443% persulfate aqueous solution once, wherein mass ratio is every part of shell pre-emulsion: seed emulsion: persulfate aqueous solution total amount=18～25; 240～244:36.15 is incubated 1 hour afterwards again, reduces to 40 ℃ of dischargings, promptly gets the silicon dioxide-acrylate copolymer emulsion.
2, the preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive according to claim 1, it is characterized by the nano silicon water-sol of step described in 1. and be commercially available silica hydrosol product or use as polishing fluid after silica hydrosol after filtering through 300 eye mesh screens, its solid content is 42%～45%, and particle diameter is between 40～95nm.
3, the preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive according to claim 1, it is characterized by step 2. described in every part of shell monomers acrylic acid content be that mass ratio is a vinylformic acid: every part of shell monomers=3:120.
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