CN103320077B - Organosilicon modified high-strength polyester hot melt adhesive - Google Patents
Organosilicon modified high-strength polyester hot melt adhesive Download PDFInfo
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- CN103320077B CN103320077B CN201310193616.0A CN201310193616A CN103320077B CN 103320077 B CN103320077 B CN 103320077B CN 201310193616 A CN201310193616 A CN 201310193616A CN 103320077 B CN103320077 B CN 103320077B
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- melt adhesive
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- phenyl silicone
- silicone resin
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Abstract
The invention relates to a hot melt adhesive composition. The hot melt adhesive composition comprises a polyester hot melt adhesive and a methylphenyl silicone resin component, and also comprises butyltindilaurate and tetraethyl orthosilicate or phenyl silicone oil. Straight-chain polyester and a silicone resin form an interpenetrating network through adding an organosilicon group to modified polyester, so the chemical structure of a chain polyester resin is changed, thereby the thermal property and adhesion strength of polyester are improved. The obtained modified hot melt adhesive composition has an adhesion strength reaching above 10MPa, a softening point temperature reaching 220DEG C, and can well bond with a metal composite plate after high and low temperature cycle (between 85DEG and -25DEG C) 10 times. The hot melt adhesive can satisfy the cementation requirement of a service workpiece at 200DEG C.
Description
Technical field
Invention relates to the composition that contains polyester or polyester hot-melt adhesive and methyl phenyl silicone resin, particularly between metal sheet or the hot-melt adhesive composition boning between metal sheet and macromolecular material.
Background technology
Ply-metal (band) refers in layer of metal coated with another metal sheet, can under the prerequisite that does not reduce result of use (decorate properties, antiseptic property, physical strength etc.), economize on resources, reduce costs.The general hot melt adhesive that uses carries out the compound of two metal plates (band), requires to have for compound hot melt adhesive the ability that higher cohesive strength, high temperature resistant, acid and alkali-resistance and other chemical reagent corrode.Polyester hot-melt adhesive is better to the bond effect of metal and high molecular polymer, and can meet different actual demands from proportioning by adjusting composition sour and alcohol in raw material.In US Patent No.-4352958, US-4146586, ethylene vinyl acetate is joined and in polyester hot-melt adhesive, carries out modification, although ethylene vinyl acetate add the cohesive strength that can improve hot melt adhesive, the softening temperature of polyester hot-melt adhesive reduces, acid-proof alkaline does not improve.Polyester or polyester hot-melt adhesive are linear saturated polyester's materials, lack crosslinked center, cause that its softening temperature is low, acid-proof alkaline is poor.
Summary of the invention
Technical problem to be solved by this invention is: polyester hot-melt adhesive is carried out to modification, to improve softening point temperature and the cohesive strength of polyester hot-melt adhesive.
An organic-silicon-modified high-strength polyester hot melt adhesive, includes following component by weight: polyethylene terephthalate, methyl phenyl silicone resin, initiator, solidifying agent; Described polyethylene terephthalate and the weight ratio of methyl phenyl silicone resin are 7:3～9:1; The weight of described initiator is 1% of methyl phenyl silicone resin weight; The weight of described solidifying agent is 3～9% of methyl phenyl silicone resin weight.
Above-mentioned initiator is preferably from two lauric acid butyl tin; Above-mentioned solidifying agent is preferably from tetraethoxy or phenyl silicone oil.
This polyester hot-melt adhesive can be prepared by the following method: polyethylene terephthalate, methyl phenyl silicone resin, initiator, solidifying agent are mixed, then 200～230 ℃ of temperature range reacting by heating 0.5～1 hour, obtain.
Generally, when using this polyester hot-melt adhesive, can be made into micelle or glued membrane, be placed in and need hot-pressing processing on bonding workpiece.
Methyl phenyl silicone resin and polyethylene terephthalate have good compatibility and acid-proof alkaline, are not subject to the impact of salt, alcohol, oil.The present invention carries out modification by methyl phenyl silicone resin and other auxiliary agent to polyethylene terephthalate, improves softening point temperature and the intensity of polyester hot-melt adhesive.Wherein, methyl phenyl silicone resin is properties-correcting agent, is aided with solidifying agent and initiator.Silicone resin main chain is Si-O-Si, belongs to inorganic structure, and its bond energy is far above C-C key bond energy, thereby it has good thermotolerance.Methyl phenyl silicone resin is joined in polyester hot-melt adhesive, with polyester hot-melt adhesive blend, add initiator, for example: two lauric acid butyl tin, then add solidifying agent tetraethoxy or phenyl silicone oil.In polyester hot-melt adhesive, add silicone resin to be conducive to improve hot melt adhesive thermotolerance, but methyl phenyl silicone resin itself is limited to the cohesive strength contribution of metal, the content that therefore limits methyl phenyl silicone resin in hot-melt adhesive composition is that the content of 10～30%, two lauric acid butyl tin is methyl phenyl silicone resin 1%, tetraethoxy and phenyl silicone oil content are 1～9% of methyl phenyl silicone resin weight.
technique effect
Adopt hot melt adhesive of the present invention, adopt methyl phenyl silicone resin to carry out modification to polyester, the polyester hot-melt adhesive obtaining can reach 10MPa for metal sheet cohesive strength, and softening point temperature reaches 220 ℃.And conventional polyester hot-melt adhesive, cohesive strength is generally at 6MPa, and softening point temperature is generally at 70～170 ℃.
The average softening point temperature of the polyester hot-melt adhesive that methyl phenyl silicone resin, two lauric acid butyl tin, tetraethoxy modification obtain is 178 ℃; The average softening point temperature of polyester hot-melt adhesive that methyl phenyl silicone resin, two lauric acid butyl tin, phenyl silicone oil modification obtain is 220 ℃.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of polyester hot melt adhesive;
Fig. 2 is the infared spectrum of methyl phenyl silicone resin;
Fig. 3 is the infared spectrum of methyl phenyl silicone resin add-on while being 30%;
Fig. 4 is bimetal bonding sample structure.
Embodiment
embodiment 1
By weight, by 30 parts of methyl phenyl silicone resins, 70 parts of polyester hot-melt adhesives (polyethylene terephthalate, PET), 0.3 part of two lauric acid butyl tin, 0.9 part of phenyl silicone oil mix; Be put in crucible, then the crucible that holds sample is placed on electric heating panel and is heated, control the temperature of hot-plate, constantly use the hot melt adhesive in glass stick stirring crucible, prevent that excess Temperature from causing hot melt adhesive zoom, affect its various performances, at 210 ℃ of temperature, reacting by heating 0.5 hour, obtains.
Fig. 1 is the infared spectrum of polyethylene terephthalate, and Fig. 2 is the infrared spectrum of methyl phenyl silicone resin, and Fig. 3 is the infared spectrum of the polyester hot-melt adhesive for preparing while being 30% of methyl phenyl silicone resin add-on.In Fig. 2,3750cm
-1and 3630cm
-1belong to free-OH absorption peak in Si-OH; 3600～3200 cm
-1peak belong to Si-OH stretching vibration absorption peak; 2965 cm
-1place is C-H stretching vibration absorption peak in Me-Si; 1700～2000 cm
-1between a series of weak absorption peak frequency multiplication peak that is monosubstituted phenyl; At 1431 cm
-1locating strong and sharp-pointed absorption peak, is the absorption of vibrations of aromatic ring in Si-Ph; At 1260 cm
-1the absorption peak that place is strong and sharp, belongs to the flexural vibration of Me in Si-Me; At 1000～1300 cm
-1locating wide and strong absorption band, is the antisymmetric stretching vibration of Si-O-Si, is also the charateristic avsorption band of silicone resin; At 803 cm
-1the absorption peak at place is Si-Me rocking vibration; 725 cm
-1with 699 cm
-1charateristic avsorption band for side chain monosubstituted phenyl.Visible, this is to contain the methylphenylsiloxane of holding light base.
After modification, the infared spectrum of blend shows as Fig. 3.Through examination of infrared spectrum analysis, find, in the composition of polyester hot-melt adhesive that the present invention prepares, occurred silicon hydroxyl characteristic peak, illustrate and in modified poly ester, be mixed into organosilicon radical.Polyester hot-melt adhesive after modification is at wave number 3600～3200cm
-1between the flexible absorption peak of Si-OH die down, the hydroxyl in this explanation silicone resin intermediate reacts in heating blend, 1210～1160cm
-1between C-(C=O)-O absorption peak also more unmodified polyester hot melt adhesive strengthen to some extent, illustrate that the hydroxyl quantity after modification reduces to some extent.This explanation polyester and methyl phenyl silicone resin occur to hold mutually, form interpenetrating(polymer)networks, change chain vibrin chemistry mechanism, thereby have improved resistance toheat and the cohesive strength of polyester.
In use, this polyester hot-melt adhesive can be made into micelle or glued membrane according to the difference of applicable situation technique, is to be generally prepared into glued membrane to be overlying on and on the metal sheet of handling well, to carry out hot-pressing processing.
Softening temperature testing method: the softening temperature test of hot melt adhesive is all to adopt ring and ball method to measure, its principle is that the certain steel ball of quality is placed on the metal ring that fills up hot melt adhesive sample, temperature rise rate according to the rules heats, after reaching certain temperature, steel ball can be absorbed in sample, then softening hot melt adhesive together falls with steel ball, and the temperature when steel ball touches underlying metal floor is considered as the softening temperature of sample.The polyester hot-melt adhesive that the present embodiment is prepared carries out softening temperature test, and when being warming up to 250 ℃, steel ball does not still drop, and can think that the temperature of its softening temperature is greater than 250 ℃.
Bond strength testing method: test button is processed according to the testing method of GB GB 7124-86, cuts into matrix metal the strip tinsel of 100 mm * 25 mm.Sample bonding mode and size are as shown in Figure 4.
Hot melt adhesive is brushed equably on metal testing plate surface, surface covered (12.5 ± 0.5) mm * 25 mm, it is bonding that two metal testing plates are taken by this length list, imposes certain pressure, guarantee bonding firmly.Tackiness agent is 25 ℃ of room temperatures, fully dry under relative humidity 30% condition, and on RGM-4050 type microcomputer controlled electronic universal tester carry out tensile shear(ing) test after h set times 24, with the speed of 5 ± 1mm/min, stablizes loading.
The tensile shear strength of metallic bone sample calculates by following formula: τ=P/ (BL)
In formula,
The tensile shear strength of τ-sizing agent, MPa;
P-sample is sheared the maximum load of broken ring, N;
B-sample faying surface width, mm;
L-sample faying surface length, mm.
Five parallel samples of each data point test, then average.
The cohesive strength of the polyester hot-melt adhesive that the present embodiment makes is 15.4MPa.
In addition, due to sizing agent and different by the linear expansivity of sticky material, after alternating hot and cold circulates several times, glue-line, with the sticky material of quilt, repeatedly pucker & bloat occurs to be changed, and will, glueing joint edge generation stress concentration, likely can affect bonding property.
Therefore, investigate further the high and low temperature cycle performance test after using above-mentioned polyester hot-melt adhesive bonding to workpiece.This bonding workpiece is carried out after high cold cycle (between 85 ℃ and-25 ℃) 10 times, and composite metal plate is in conjunction with good.This bonding workpiece is maintained after 1h in 85 ± 1 ℃, in-25 ℃ ± 2 ℃, maintain 1h again, altogether carry out 10 circulations, sample is not all peeled off, because polyester hot-melt adhesive itself has the performance of good cold-hot circulation, after modification, do not make the performance of its cold-hot circulation reduce, the polyester hot-melt adhesive after modification has good over-all properties
embodiment 2
By 30 parts of methyl phenyl silicone resins, 70 parts of polyester hot-melt adhesives (polyethylene terephthalate, PET), 0.3 part of two lauric acid butyl tin, 1.5 parts of tetraethoxys mix, products obtained therefrom softening temperature is greater than 250 ℃, cohesive strength is 12.3MPa.
embodiment 3
By 30 parts of methyl phenyl silicone resins, 70 parts of polyester hot-melt adhesives, (polyethylene terephthalate, PET), 0.3 part of two lauric acid butyl tin, 2.1 parts of tetraethoxys mix, at 200 ℃ of temperature, reacting by heating 0.5 hour, obtains.Products obtained therefrom softening temperature is greater than 250 ℃, and cohesive strength is 11.9MPa.
embodiment 4
By 30 parts of methyl phenyl silicone resins, 70 parts of polyester hot-melt adhesives, (polyethylene terephthalate, PET), 0.3 part of two lauric acid butyl tin, 2.7 parts of phenyl silicone oil mix, at 230 ℃ of temperature, reacting by heating 1 hour, obtains.Products obtained therefrom softening temperature is greater than 250 ℃, and cohesive strength is 10.9MPa.
embodiment 5
By 20 parts of methyl phenyl silicone resins, 80 parts of polyester hot-melt adhesives, (polyethylene terephthalate, PET), 0.2 part of two lauric acid butyl tin, 0.9 part of phenyl silicone oil mix, at 220 ℃ of temperature, reacting by heating 0.6 hour, obtains.Products obtained therefrom softening temperature is greater than 250 ℃, and cohesive strength is 13.8MPa.
embodiment 6
By 10 parts of methyl phenyl silicone resins, 90 parts of polyester hot-melt adhesives, (polyethylene terephthalate, PET), 0.1 part of two lauric acid butyl tin, 0.9 part of phenyl silicone oil mix, at 230 ℃ of temperature, reacting by heating 0.8 hour, obtains.Products obtained therefrom softening temperature is greater than 250 ℃, and cohesive strength is 10.5MPa.
The polyester hot-melt adhesive of embodiment 2～6 gained is carried out as identical high low temperature cycle performance test in embodiment 1 to the situation that test piece all must sample not be peeled off.
Claims (3)
1. an organic-silicon-modified high-strength polyester hot melt adhesive, is characterized in that, includes following component by weight: polyethylene terephthalate, methyl phenyl silicone resin, initiator, solidifying agent; Described polyethylene terephthalate and the weight ratio of methyl phenyl silicone resin are 7:3～9:1; The weight of described initiator is 1% of methyl phenyl silicone resin weight; The weight of described solidifying agent is 3～9% of methyl phenyl silicone resin weight; Described solidifying agent is tetraethoxy or phenyl silicone oil.
2. organic-silicon-modified high-strength polyester hot melt adhesive according to claim 1, is characterized in that: described initiator is two lauric acid butyl tin.
3. the preparation method of the organic-silicon-modified high-strength polyester hot melt adhesive described in claim 1～2 any one, the steps include: polyethylene terephthalate, methyl phenyl silicone resin, initiator, solidifying agent to mix, 200～230 ℃ of temperature range reacting by heating 0.5～1 hour, obtain again.
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| CN201310193616.0A CN103320077B (en) | 2013-05-22 | 2013-05-22 | Organosilicon modified high-strength polyester hot melt adhesive |
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| CN201310193616.0A CN103320077B (en) | 2013-05-22 | 2013-05-22 | Organosilicon modified high-strength polyester hot melt adhesive |
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| CN103320077B true CN103320077B (en) | 2014-10-22 |
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| CN106189981A (en) * | 2016-07-21 | 2016-12-07 | 河海大学 | A kind of metal composite and photovoltaic component encapsulating polyester hot-melt adhesive and preparation method thereof |
| US20190284444A1 (en) * | 2016-11-28 | 2019-09-19 | 3M Innovative Properties Company | An adhesive composition and an adhesive film obtained therefrom |
| CN109161171A (en) * | 2018-08-23 | 2019-01-08 | 江苏新光环保工程有限公司 | A kind of preparation method of porous aluminum acoustic board |
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