CN102660205A - Acrylate hot melt adhesive composition and preparation method of hot melt adhesive by UV (ultraviolet) crosslinking - Google Patents
Acrylate hot melt adhesive composition and preparation method of hot melt adhesive by UV (ultraviolet) crosslinking Download PDFInfo
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- CN102660205A CN102660205A CN2012101782967A CN201210178296A CN102660205A CN 102660205 A CN102660205 A CN 102660205A CN 2012101782967 A CN2012101782967 A CN 2012101782967A CN 201210178296 A CN201210178296 A CN 201210178296A CN 102660205 A CN102660205 A CN 102660205A
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- hot melt
- melt adhesive
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000004132 cross linking Methods 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 7
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 34
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- 238000000034 method Methods 0.000 claims description 11
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Images
Abstract
The invention belongs to the technical field of a hot melt adhesive, and particularly relates to an acrylate hot melt adhesive composition and a preparation method of a hot melt adhesive by UV (ultraviolet) crosslinking. The composition of the acrylate hot melt adhesives comprises the following components based on weight content ratio: 9-90% of acrylate copolymer, 9-90% of copolyester and 0.1-1% of antioxidant. The preparation method of the hot melt adhesive by UV crosslinking comprises the following specific steps of: polymerizing at least one of acrylate monomer bodies; and adding the composition into a double-screw extruder to carry out high-speed mixing, in-situ grafting, compatibilization and chain extension, coating a base material by means of hot melting at the temperature of 130-160 DEG C, carrying out ultraviolet light crosslinking, and packing in a rolling way. The preparation method has the benefit effects that part of hot melt adhesive is crosslinked by means of UV crosslinking, so that the cohesive strength of the hot melt adhesive can be improved, and the glue-overflowing performance can be resistant, and the joint strength can be improved. Meanwhile, the hot melt adhesive provided by the invention is further added with copolyester with equivalent quantity besides the main body resin, and the higher wettability, cohesive strength and heat resistance, and good weather fastness can be obtained due to the introduction of the copolyester.
Description
Technical field
The invention belongs to the hot melt adhesive technical field, be specifically related to a kind of preparation method of compsn and UV cross linked acrylic hot melt adhesive of acrylic esters hot-melt glue.
Background technology
Hot melt adhesive (Hot Melt Adhesive) be a kind of be the multicomponent mixture of matrix with the thermoplastics; It is applied to substrate surface with melt form and carries out bonding; It is solid-state at normal temperatures, is fused into liquid state after the heating, the coating, wetting bonded after; Through pressing cooling, in several seconds even shorter time, can realize bonding.Hot melt adhesive and thermoset, solvent-borne type, water-based adhesive are different, do not contain any solvent, can not pollute because of solvent evaporates; Without heat cross-linking, the no drying process, easy to use; Can be made into bulk, film like, strip or granular; Make packing, accumulating and use all comparatively convenient, can satisfy discontinuous production line operation requirement, can be applied on the high-speed and continuous production line again.
At present, the main body in hot melt adhesive market is an EVA type hot melt adhesive, account for about 80% of hot melt adhesive total quantity consumed, but its cohesive strength is low, and is thermo-labile, can not be used as the electron trade structure glue.Expansion along with the hot melt adhesive Application Areas; Some new type hot-melt adhesives begin to occur and be able to development; Comprise (methyl) esters of acrylic acid, polyethylene kind, Atactic Polypropelene class, polyamide-based, polyimide, ethene-(methyl) vinylformic acid second (fourth) ester copolymer resins class, polyester, polyurethanes and some other rubber/plastics block interpolymers etc.
The esters of acrylic acid tackiness agent have raw material sources extensively, be prone to synthetic, good endurance, low-temperature performance is good, the transparency is good, nontoxic and non-environmental-pollution, manufacturing and do not have fire hazard, bonding wide, characteristics such as adhesiveproperties is good when storing and transporting basically.Yet polyacrylic ester was both non-crystallizable; Also bigger cohesive strength is arranged when cooling off unlike traditional hot-melt adhesive; At present acrylic esters hot-melt glue is not enough because of its crosslinking degree, Joint strength is low, temperature tolerance difference and high temperature hot pressing are prone to overflow defectives such as glue, applies difficulty in electron trade.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming of existing acrylic esters hot-melt glue, provide a kind of partial cross-linked, Joint strength is high, the compsn of the acrylic esters hot-melt glue of the glue that do not overflow in good heat resistance and the high temperature hot pressing bonding process.
Second purpose of the present invention is to provide the preparation method of UV cross linked acrylic hot melt adhesive.
For realizing above-mentioned purpose; The present invention adopts two technical schemes; These two schemes comprise the technical identical specified features that is mutually related---and the compsn that forms UV cross linked acrylic hot melt adhesive constitutes; Therefore two technical schemes belong to a total inventive concept, meet the unicity requirement.
In order to realize first purpose; The technical scheme that the present invention adopts is: the compsn of acrylic esters hot-melt glue is characterized in that: said composition comprises the component of following mass content ratio: Yodo Sol GH 28 9-90%, copolyesters 9-90%, oxidation inhibitor 0.1-1%, initiator 0.1-1%; The weight-average molecular weight of Yodo Sol GH 28 is 50000～300000g/mol, and second-order transition temperature is not higher than 20 ℃, and melt viscosity is 10-70Pa.S in the time of 160 ℃.
The compsn of aforesaid acrylic esters hot-melt glue, described Yodo Sol GH 28 contains following component by mass percent: structural unit SY-Monomer G 1-10%; Contain vinyl group or methacrylate based group to UVNUL MS-40 0.5-5%; Also comprise one or more of following structural unit, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi and Isooctyl acrylate monomer in the structural unit of multipolymer.
The compsn of aforesaid acrylic esters hot-melt glue, described copolyesters contains the structural unit of following mass percent: the dimer 10-50%, 2 of polyunsaturated vegetable oil acid, 4-diethylammonium-1,5-pentanediol (DEPD) 5-30%, dimer diols 5-50%.
The compsn of aforesaid acrylic esters hot-melt glue, the second-order transition temperature of said copolyesters are not higher than-20 ℃, and molecular weight is 8～200,000 g/mol, and melt viscosity is 20～100Pa.S in the time of 160 ℃.
The compsn of aforesaid acrylic esters hot-melt glue; Described oxidation inhibitor is four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3; The 5-di-t-butyl) the positive octadecanol ester of propionic acid, DBPC 2,6 ditertiary butyl p cresol, 4, one or more of 4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol).
For realizing second purpose, the technical scheme that the present invention adopted is: the preparation method of UV cross linked acrylic hot melt adhesive comprises following concrete steps: Yodo Sol GH 28 and copolyesters synthetic respectively; The compsn of Yodo Sol GH 28 and copolyesters formation is added twin screw extruder mixed at high speed, situ-formed graft, increase-volume chain extension, and at 130 ℃ of-160 ℃ of heat seeling coating base materials, ultraviolet light cross-linking, rolling packing.
The preparation method of aforesaid UV cross linked acrylic hot melt adhesive, described situ-formed graft, increase-volume chain extension gained hot melt adhesive, the melt composition melt viscosity was controlled at 20～100Pa.S when extrusion temperature was 160 ℃.
The preparation method of aforesaid UV cross linked acrylic hot melt adhesive, described mixed at high speed, coating, ultraviolet light cross-linking, rolling step are carried out on transmission mechanism continuously, and described ultraviolet light cross-linking step is accomplished by UV lamp, UV Measurement and Control System.
Beneficial effect of the present invention: back the present invention adopts the crosslinked hot melt colloid molecule (intramolecularly or intermolecular) that makes of UV crosslinked in the hot melt adhesive coating; Improved hot melt colloidal internal cohesive energy to improve crosslinking degree; Hot melt adhesive of the present invention also adds the dimer acid type copolyesters of a great deal of except that matrix resin simultaneously; The introducing of dimer acid type copolyesters can obtain excellent bond performance, and the introducing of dimer acid type copolyesters can obtain higher thermotolerance, good weather-proof, water tolerance and elasticity.
Description of drawings
Fig. 1 is preparing method's schema of UV cross linked acrylic hot melt adhesive of the present invention;
Fig. 2 is UV cross linked acrylic hot melt adhesive coating of the present invention, UV-crosslinked and wrapup procedure synoptic diagram;
Wherein, 1 extruder head, 2 dispense tips, 3 rolling-up mechanisms, the 4UV lamp, the 5UV Measurement and Control System, 6 colloids are molecule crosslinked, 7 melting heat melten gels.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is further described: wherein, 1 extruder head, 2 dispense tips, 3 rolling-up mechanisms, the 4UV lamp, the 5UV Measurement and Control System, 6 colloids are molecule crosslinked, 7 melting heat melten gels.
What deserves to be mentioned is; The used whole reagent raw materials of the present invention; The monomer, the monomer of copolyesters, oxidation inhibitor, the initiator that comprise Yodo Sol GH 28 can be bought perhaps independently synthetic through buying the relevant monomer raw material through the commercialization approach; The synthetic technical matters is known by those skilled in the art, does not therefore describe in detail.In addition, the present invention prepares technology related in the process (mixed at high speed, situ-formed graft, increase-volume chain extension, heat seeling coating etc.) at hot melt adhesive and is those skilled in the art and knows, and does not therefore describe in detail.
The compsn of acrylic esters hot-melt glue is characterized in that, said composition comprises the component of following mass content ratio: Yodo Sol GH 28 10-90%, copolyesters 10-90%, oxidation inhibitor 0.1-1%, light trigger 0.1-1%; The weight-average molecular weight of Yodo Sol GH 28 is 50000～300000g/mol, and second-order transition temperature is not higher than 20 ℃, and melt viscosity is 10-70Pa.S in the time of 160 ℃.Oxidation inhibitor is four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3; The 5-di-t-butyl) the positive octadecanol ester of propionic acid, DBPC 2,6 ditertiary butyl p cresol, 4, one or more of 4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol); Add oxidation inhibitor and can guarantee that adhesiveproperties does not change under hot conditions.Described initiator comprises one or more of unit molecule cracking type initiator such as Benzoin ethyl ether, hydrogen extraction type initiator such as various initiators such as UVNUL MS-40, energy transfer initiator such as thioxanthone, ionic reaction type initiator such as diaryl group iodized salt, is used for auxiliary heat melten gel molecule crosslinked under UV irradiation.
The preparation method of UV cross linked acrylic hot melt adhesive; It is characterized in that: this method will cause the Yodo Sol GH 28 and the composite hot-melt adhesive composition that obtains of copolyesters of functional group with UV-light, and said composition makes partial cross-linked hot melt adhesive through UV-crosslinked again through heat seeling coating.
Structural unit SY-Monomer G 1-10% in the Yodo Sol GH 28, optimum proportion is 3-5%; Contain vinyl group or (methyl) acrylate group to UVNUL MS-40 0.5-5%, optimum proportion is 1-3%, vinyl or (methyl) are acrylate-based mainly in contraposition, (methyl) is acrylate-based to link to each other with phenyl ring through phenol oxygen key; Other copolymerization structural unit of Yodo Sol GH 28 also comprises one or more in the following monomer, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi and (methyl) Isooctyl acrylate monomer.More than be weight percentage.
Explain that below in conjunction with embodiment 1-4 the band UV-light that contains initiator causes the preparation process of the Yodo Sol GH 28 of functional group.
Embodiment 1
Get 42 parts of ethyl propenoates, 49 parts of Bing Xisuandingzhis by weight percentage, 3 parts (epoxide group is used for carrying out chain extending reaction with the carboxyl of copolyesters SY-Monomer G; Reduce the hydrolysis of copolyesters simultaneously), 0.5 part of 1 part of 4-vinyl-4-methoxy benzophenone (the UV initiating group produces radical after the cracking), 5 parts of Isooctyl acrylate monomers, 150 parts of solvent vinyl acetic monomers and initiator Diisopropyl azodicarboxylate.Material is added in the four-hole boiling flask; Four-hole boiling flask is equipped with TM, reflux condensing tube, whisking appliance and nitrogen conduit temperature; System under nitrogen protection 62 ℃ carried out copolymerization 6 hours, then 76 ℃ of following copolymerization 8 hours, obtain the Yodo Sol GH 28 solution of 40% solids content.Then, under the lucifuge condition, copolymer solution is painted the 0.150mm thick layer with scraper, dry out solvent and residual monomer obtain copolymer adhesive film under the lucifuge condition then.The weight-average molecular weight that records this Yodo Sol GH 28 is 200,000 g/mol, and second-order transition temperature is-29 ℃, and in the time of 160 ℃, melt viscosity is 25Pa.S.Wherein in the solid, the weight content of SY-Monomer G is 3%, and the weight content of 4-vinyl-4-methoxy benzophenone is 1%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.5%.
Get 0.4 part of 42 parts of ethyl propenoates, 47 parts of Bing Xisuandingzhis, 3 parts of SY-Monomer Gs, 4-vinyl-3 parts of 4-methoxy benzophenones, 5 parts of Isooctyl acrylate monomers, 150 parts of solvent vinyl acetic monomers and initiator Diisopropyl azodicarboxylate by weight percentage.Adopt the technology of embodiment 1 to make copolymer adhesive film.The weight-average molecular weight that records this Yodo Sol GH 28 is 290,000 g/mol, and second-order transition temperature is-25 ℃, and in the time of 160 ℃, melt viscosity is 31Pa.S.Wherein in the solid, the weight content of SY-Monomer G is 3%, and the weight content of 4-vinyl-4-methoxy benzophenone is 3%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.4%.
Embodiment 3
Get 0.4 part of 20 parts of Jia Jibingxisuanyizhis, 43 parts of NSC 20956s, 3 parts of SY-Monomer Gs, 4-vinyl-3 parts of 4-methoxy benzophenones, 30 parts of Isooctyl acrylate monomers, 150 parts of solvent vinyl acetic monomers and initiator Diisopropyl azodicarboxylate by weight percentage.Adopt the technology of embodiment 1 to make copolymer adhesive film.The weight-average molecular weight that records this Yodo Sol GH 28 is 230,000 g/mol, and second-order transition temperature is 4 ℃, and in the time of 160 ℃, melt viscosity is 43Pa.S.Wherein in the solid, the weight content of SY-Monomer G is 3%, and the weight content of 4-vinyl-4-methoxy benzophenone is 3%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.4%.
Embodiment 4
Get 0.4 part of 20 parts of Jia Jibingxisuanyizhis, 44 parts of Bing Xisuandingzhis, 3 parts of SY-Monomer Gs, 4-vinyl-3 parts of 4-methoxy benzophenones, 30 parts of Isooctyl acrylate monomers, 150 parts of solvent vinyl acetic monomers and initiator Diisopropyl azodicarboxylate by weight percentage.Adopt the technology of embodiment 1 to make copolymer adhesive film.The weight-average molecular weight that records this Yodo Sol GH 28 is 230,000 g/mol, and second-order transition temperature is-27 ℃, and in the time of 160 ℃, melt viscosity is 34Pa.S.Wherein in the solid, the weight content of SY-Monomer G is 3%, and the weight content of 4-vinyl-4-methoxy benzophenone is 3%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.4%.
Copolyesters contains structural unit dimeracid (like the vegetable oil acid dimer), and mass percent is 10-50%, and optimum proportion is 10-25%; The structural unit that copolyesters contains divalent alcohol is 2,4-diethylammonium-1, and 5-pentanediol (DEPD), mass percent is 5-30%, optimum proportion is 10-15%.Described copolyesters contains structural unit dimer diols (dimeracid hydrogenation gained, the Pripol 2033 of Uniqema company), and mass percent 5-50%, optimum proportion are 10-25%; Also possibly contain 1,6-pinakon, 2,4-diethylammonium-1,5-pentanediol.The second-order transition temperature of copolyesters is not higher than-20 ℃, and molecular weight is 3000～35000g/mol, and melt viscosity is 5～600Pa.S in the time of 160 ℃.
The preparation process that contains the copolyesters of oxidation inhibitor below in conjunction with embodiment 5-8 explanation.
Divalent alcohol: 14.3 moles of butyleneglycols, 1,5.72 moles of 6-pinakons and 2,4-diethylammonium-1,11.44 moles of 5-pentanediols (DEPD).Diprotic acid raw material: 2.83 moles of 15.56 moles of DMT. Dimethyl p-benzenedicarboxylates, vegetable oil acid dimer and 1,9.91 moles of 6-hexanodioic acids.The esterifying catalyst and the 10 gram oxidation inhibitor that add 3 grams in addition.Earlier divalent alcohol is added the reaction kettle of the esterification of 10L, reaction kettle is equipped with TM, reflux condensing tube, whisking appliance and distiller, and system is warming up to 140 ℃ under nitrogen protection.Then diprotic acid and catalyzer are added in the esterifying kettle, are warmed up to 235 ℃ and carry out esterification, in the distillation sundries till the no product.At last, be warming up to 250 ℃, to the vacuum operating that carries out of reaction kettle of the esterification, until the vacuum tightness of reaction kettle less than 1mbar.The reaction product that takes a morsel is painted the 0.150mm thick layer with scraper, carries out analytical test.The second-order transition temperature of copolyesters-27 ℃, the melt viscosity of copolyesters is 12Pa.S/160 ℃.Wherein, the weight content of oxidation inhibitor is 0.2%.
Instance 6
Divalent alcohol: 11.3 moles of butyleneglycols, 1,5.72 moles of 6-pinakons and 2,4-diethylammonium-1,14.44 moles of 5-pentanediols (DEPD).Diprotic acid raw material: 2.83 moles of 15.56 moles of DMT. Dimethyl p-benzenedicarboxylates, vegetable oil acid dimer and 1,9.91 moles of 6-hexanodioic acids.The esterifying catalyst and the 10 gram thermo-stabilizers that add 3 grams in addition.Preparation technology is with instance 5.The second-order transition temperature of copolyesters-24 ℃, the copolyesters melt viscosity is 10.3Pa.S/160 ℃.Wherein, the weight content of oxidation inhibitor is 0.3%.
Divalent alcohol: 11.3 moles of butyleneglycols, 1,5.72 moles of 6-pinakons and 2,4-diethylammonium-1,14.44 moles of 5-pentanediols (DEPD).Diprotic acid raw material: 6.39 moles of 12 moles of DMT. Dimethyl p-benzenedicarboxylates, vegetable oil acid dimer and 1,9.91 moles of 6-hexanodioic acids.The esterifying catalyst and the 10 gram thermo-stabilizers that add 3 grams in addition.Preparation technology is with instance 5.The second-order transition temperature of copolyesters-42 ℃, the copolyesters melt viscosity is 9.7Pa.S/160 ℃.Wherein, the weight content of oxidation inhibitor is 0.2%.
Instance 8
Divalent alcohol: 11.3 moles of butyleneglycols, 1,5.72 moles of 6-pinakons and 2,4-diethylammonium-1,14.44 moles of 5-pentanediols (DEPD).Diprotic acid raw material: 6.39 moles of 15.56 moles of DMT. Dimethyl p-benzenedicarboxylates, vegetable oil acid dimer and 1,6.35 moles of 6-hexanodioic acids.The esterifying catalyst and the 10 gram thermo-stabilizers that add 3 grams in addition.Preparation technology is with instance 5.The second-order transition temperature of copolyesters-31 ℃, the melt viscosity of copolyesters is 11Pa.S/160 ℃.Wherein, the weight content of oxidation inhibitor is 0.2%.
The preparation method of UV cross linked acrylic hot melt adhesive comprises following concrete steps: one or more acrylate monomer mass polymerizations are also added initiator; The polymerization of copolyesters; The compsn of Yodo Sol GH 28 and copolyesters formation is added twin screw extruder mixed at high speed, situ-formed graft, increase-volume chain extension, and at 130 ℃ of-160 ℃ of heat seeling coating base materials, ultraviolet light cross-linking, rolling packing.Situ-formed graft, increase-volume chain extension gained hot melt adhesive, the melt composition melt viscosity was controlled at 10～100Pa.S when extrusion temperature was 160 ℃.Mixed at high speed, coating, ultraviolet light cross-linking, rolling step are carried out on transmission mechanism continuously, and described ultraviolet light cross-linking step is accomplished by UV lamp, UV Measurement and Control System.
Existing hot melt adhesive cohesive strength is low, Joint strength is not enough in order to overcome, the shortcoming of the glue that is prone in the poor heat resistance, bonding process to overflow; After compsn of the present invention is processed hot melt adhesive coating, under UV-light (UV), on the Yodo Sol GH 28 molecular side chain to the UVNUL MS-40 group activation; Capture the Wasserstoffatoms of tertiary carbon atom on this high-polymer molecular chain; The carbon atom that while carbonyl carbon atom links to each other with Wasserstoffatoms combines, and generates carbon carbon saturated bond and hydroxyl, and crosslinking reaction is accomplished.Through regulating the concentration of p-Xylol ketone in the Yodo Sol GH 28, can control the degree of crosslinking of final hot melt adhesive film.The crosslinked hot melt colloid molecule (intramolecularly or intermolecular) that makes is partial cross-linked; Improved hot melt colloidal internal cohesive energy; Improved initial bonding strength; Simultaneously hot melt adhesive of the present invention also adds the dimer acid type copolyesters of a great deal of except that matrix resin, and the introducing of dimer acid type copolyesters can obtain excellent bond performance, resistance is good, and the introducing of dimer acid type copolyesters can obtain higher thermotolerance, good weather-proof, water tolerance and elasticity.
Above-mentioned compsn comprises Yodo Sol GH 28, copolyesters, oxidation inhibitor, initiator; Described compsn is added the twin screw extruder mixed at high speed situ-formed graft, increase-volume chain extending reaction take place simultaneously; Grafting, chain extending reaction occur between the hydroxyl, carboxyl of Yodo Sol GH 28 epoxy group(ing) and copolyesters; Copolyesters also connects together through Yodo Sol GH 28 each other, obtains the hot melt colloid; Hot melt adhesive gets into the hot melt adhesive trunnion with heating function through volume pump; The melt viscosity of compsn is at 20～100Pa.S when controlling 160 ℃, at 130 ℃ of-160 ℃ of heat seeling coatings in base material; Light is solid under ultraviolet, and rolling obtains finished material, infeeds industrial chain through the cross cutting packing, and final terminal client uses on the concrete equipment.
Further, the described coating of preparation method of the present invention, ultraviolet light cross-linking, rolling step are carried out on transmission mechanism simultaneously, and described ultraviolet light cross-linking step is accomplished by UV lamp 4, UV Measurement and Control System 5.As shown in Figure 2; Be full of melting heat melten gel 7 in the extruder head 1 of heat seeling coating machine, coat base material (being separate-type paper) and hot melt adhesive is exerted pressure, make it be adhered to substrate surface through dispense tip 2; Again through transmission mechanism (comprising rolling-up mechanism 3) coating continuously; UV lamp 4 shines the base material that scribbles hot melt adhesive in the cross-linking process simultaneously, and molecule crosslinked 6 (intramolecularly or intermolecular) of colloid under the assistance of light trigger improve the hot melt adhesive internal cohesive energy.
Pass through the preparation process of embodiment 9-14 UV cross linked acrylic of the present invention hot melt adhesive below.
Embodiment 9
Get Yodo Sol GH 28 2000 grams of embodiment 1 band UV-light initiating group and chain extension group; Other gets copolyesters 3000 grams of embodiment 5 preparations; Respectively after the lucifuge fusion; Above-mentioned compsn is added twin screw extruder (length-to-diameter ratio of forcing machine is 52, and temperature is 180～150 ℃) carry out mixed at high speed, grafting and chain extension.In this process, epoxy group(ing) in the Yodo Sol GH 28 and the carboxyl reaction in the copolyesters had both been alleviated the hydrolysis of copolyesters, again different copolyesters molecular chains were connected together, and had improved the melt strength of compsn, helped being coated with into the glued membrane of different thickness.Then, hot melt adhesive gets into the hot melt adhesive trunnion with heating function through volume pump.Then with the compsn hot melt adhesive at 160 ℃ of heat seeling coatings in solidifying on the separate-type paper and under UV-light.About ultraviolet absorption wavelength region 260nm, radiation dose 25mJ/cm
2At last, rolling obtains finished material.The shearing temperature tolerance and the stripping strength of hot melt adhesive film are seen table 1.Wherein, the weight content of Yodo Sol GH 28 (not containing initiator) is 39.84%, and the weight content of copolyesters (not containing oxidation inhibitor) is 59.84%, and the weight content of initiator is 0.2%, and the weight content of oxidation inhibitor is 0.12%.
Embodiment 10
Get instance 2 Yodo Sol GH 28s 2000 grams, other gets instance 6 copolyesters 3000 grams, according to the prepared hot melt adhesive film of embodiment 9.The shearing temperature tolerance and the stripping strength of hot melt adhesive film are seen table 1.Wherein, the weight content of Yodo Sol GH 28 (not containing initiator) is 39.83%, and the weight content of copolyesters (not containing oxidation inhibitor) is 59.83%, and the weight content of initiator is 0.16%, and the weight content of oxidation inhibitor is 0.18%.
Embodiment 11
Get instance 2 Yodo Sol GH 28s 3000 grams, other gets instance 6 copolyesters 3000 grams, according to the prepared hot melt adhesive film of instance 9.The shearing temperature tolerance and the stripping strength of hot melt adhesive film are seen table 1.Wherein, the weight content of Yodo Sol GH 28 (not containing initiator) is 49.8%, and the weight content of copolyesters (not containing oxidation inhibitor) is 49.9%, and the weight content of initiator is 0.2%, and the weight content of oxidation inhibitor is 0.1%.
Embodiment 12
Get instance 3 Yodo Sol GH 28s 2000 grams, other gets instance 7 copolyesters 3000 grams, according to the prepared hot melt adhesive film of instance 9.The shearing temperature tolerance and the stripping strength of hot melt adhesive film are seen table 1.Wherein, the weight content of Yodo Sol GH 28 (not containing initiator) is 49.8%, and the weight content of copolyesters (not containing oxidation inhibitor) is 49.9%, and the weight content of initiator is 0.2%, and the weight content of oxidation inhibitor is 0.1%.
Embodiment 13
On get instance 3 Yodo Sol GH 28s 2000 gram, other gets instance 8 copolyesters 3000 grams, according to the prepared hot melt adhesive film of instance 9.The shearing temperature tolerance and the stripping strength of hot melt adhesive film are seen table 1.Wherein, the weight content of Yodo Sol GH 28 (not containing initiator) is 40%, and the weight content of copolyesters (not containing oxidation inhibitor) is 59.72%, and the weight content of initiator is 0.16%, and the weight content of oxidation inhibitor is 0.12%.
Embodiment 14
On get instance 4 Yodo Sol GH 28s 2000 gram, other gets instance 8 copolyesters 3000 grams, according to the prepared hot melt adhesive film of instance 9.The shearing temperature tolerance and the stripping strength of hot melt adhesive film are seen table 1.Wherein, the weight content of Yodo Sol GH 28 (not containing initiator) is 40%, and the weight content of copolyesters (not containing oxidation inhibitor) is 59.72%, and the weight content of initiator is 0.16%, and the weight content of oxidation inhibitor is 0.12%.
The performance test process and the result of explanation UV cross linked acrylic hot melt adhesive are as shown in table 1 below.
Testing method
The molecular weight of Yodo Sol GH 28 and copolyesters adopts gel permeation chromatography, GPC, analyzing molecules amount and distribution thereof.Analytical instrument, Symyx Rapid GPC; Solvent, THF, concentration is 1 mg/ml; The sample amount of getting, 0.25 milliliter; Kapillary nitrogen flow rate 1.8 mark condition liters/minute.
The melt viscosity of Yodo Sol GH 28, copolyesters and hot melt adhesive is according to the ASTMD3236 standard testing.Analytical instrument, DV II+type viscometer; Sample size, the 8-9 gram; The probe temperature of Yodo Sol GH 28 and copolyesters is 160 ℃, and the probe temperature of hot melt adhesive film is 210 ℃.
The performance of hot melt adhesive
The preparation of part ultraviolet light cross-linking hot melt adhesive film sample according to the method described above, with Ge Laxin separate-type paper (grammes per square metre, 80g/ ㎡; Off-type force 100g/25mm) the hot melt adhesive film sample of preparation part ultraviolet light cross-linking, thickness is 60 gram/square meters.With glued membrane be stored in leave standstill in the standard environment 48 hours to be measured, 25 ℃, 50% humidity.
The specimen preparation of commodity polyester hot-melt adhesive glue is with self-control hot melt adhesive blade coating device, Ge Laxin separate-type paper (grammes per square metre, 80g/ ㎡; Off-type force 100g/25mm) the hot melt adhesive film sample of preparation part ultraviolet light polymerization, thickness is 60 gram/square meters.With glued membrane be stored in leave standstill in the standard environment 48 hours to be measured, 25 ℃, 50% humidity.
In the test sample preparation, the heat pressure adhesive condition of hot melt adhesive and test material is 120 ℃/10s, 6KG.
(shear adhesion failure temperature is SAFT) according to ASTM D4498 standard testing to shear temperature tolerance.Size of sample, 25mm * 25mm; Load, 500g; Heat-up rate, 0.5 ℃/min.The temperature value of correspondence when the record sample comes off, the thermotolerance of hot melt adhesive film characterizes with this temperature value, and test result is seen table 1.
Stripping strength is according to the PSTC-1 standard testing.Size of sample, 25mm * 100mm; Hot pressing condition: 120 ℃/10s; Peeling rate, 300mm/min.The record hot melt adhesive is to the stainless peeling force of ABS-stainless steel, PC-ABS and ABS-.Test result is seen table 1.
Shearing resistance is according to GB 7124-86 standard testing.Testing tool, CMT4203 type puller system; Hot pressing condition: 120 ℃/10s, 22N pressure; Draw speed 5mm/min.
The composition of table 1 hot melt adhesive and The performance test results
According to table 1, the content of light-initiated functional group raises and can effectively improve the cohesive strength of hot melt adhesive; Compare with hot melt adhesive film 615 products of 3M company, the stripping strength of this patent product, heat resistance and shearing resistance all are significantly improved.
The foregoing description does not limit the present invention in any form, and all employings are equal to the technical scheme that mode obtained of replacement or equivalent transformation, all drop on protection scope of the present invention.
Claims (9)
1. the compsn of acrylic esters hot-melt glue, it is characterized in that: said composition comprises the component of following mass content ratio: Yodo Sol GH 28 9-90%, copolyesters 9-90%, oxidation inhibitor 0.1-1%, initiator 0.1-1%; The weight-average molecular weight of Yodo Sol GH 28 is 50000～300000g/mol, and second-order transition temperature is not higher than 20 ℃, and melt viscosity is 10-70Pa.S in the time of 160 ℃.
2. the compsn of acrylic esters hot-melt glue according to claim 1 is characterized in that: described Yodo Sol GH 28 contains following component by mass percent: structural unit SY-Monomer G 1-10%; Contain vinyl group or methacrylate based group to UVNUL MS-40 0.5-5%; Also comprise one or more of following structural unit, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi and Isooctyl acrylate monomer in the structural unit of multipolymer.
3. the compsn of acrylic esters hot-melt glue according to claim 1; It is characterized in that: described copolyesters contains the structural unit of following mass percent: the dimer 10-50%, 2 of polyunsaturated vegetable oil acid; 4-diethylammonium-1,5-pentanediol (DEPD) 5-30%, dimer diols 5-50%.
4. the compsn of acrylic esters hot-melt glue according to claim 1 is characterized in that: the second-order transition temperature of said copolyesters is not higher than-20 ℃, and molecular weight is 8～200,000 g/mol, and melt viscosity is 20～100Pa.S in the time of 160 ℃.
5. the compsn of acrylic esters hot-melt glue according to claim 1; It is characterized in that: described oxidation inhibitor is four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3; The 5-di-t-butyl) the positive octadecanol ester of propionic acid, DBPC 2,6 ditertiary butyl p cresol, 4, one or more of 4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol).
6.UV the preparation method of cross linked acrylic hot melt adhesive is characterized in that: this method makes partial cross-linked hot melt adhesive through UV-crosslinked again with any described compsn heat seeling coating of claim 1-5.
7. the preparation method of UV cross linked acrylic hot melt adhesive according to claim 6 is characterized in that: comprise following concrete steps: Yodo Sol GH 28 and copolyesters synthetic respectively; The compsn of Yodo Sol GH 28 and copolyesters formation is added twin screw extruder mixed at high speed, situ-formed graft, increase-volume chain extension, and at 130 ℃ of-160 ℃ of heat seeling coating base materials, ultraviolet light cross-linking, rolling packing.
8. the preparation method of UV cross linked acrylic hot melt adhesive according to claim 7 is characterized in that: described situ-formed graft, increase-volume chain extension gained hot melt adhesive, the melt composition melt viscosity was controlled at 20～100Pa.S when extrusion temperature was 160 ℃.
9. the preparation method of UV cross linked acrylic hot melt adhesive according to claim 7; It is characterized in that: described mixed at high speed, coating, ultraviolet light cross-linking, rolling step are carried out on transmission mechanism continuously, and described ultraviolet light cross-linking step is accomplished by UV lamp, UV Measurement and Control System.
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Address after: 215111 Jiangsu city of Suzhou province Wuzhong District Jinting town tile Hill Building 3 Patentee after: SUZHOU LIANKE NANO PURIFICATION TECHNOLOGY CO., LTD. Address before: Suzhou City, Jiangsu Province, Suzhou Industrial Park 215123 Xinghu Street No. 218 BioBAY A4 building 309 Patentee before: Suzhou Link Syn-Materials Co., Ltd. |
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Effective date of registration: 20170310 Address after: 231300 Lu'an, Shucheng, Hangzhou Port Economic Development Zone, Magnolia Road Patentee after: Shucheng joint surface treatment Co., Ltd. Address before: 215111 Jiangsu city of Suzhou province Wuzhong District Jinting town tile Hill Building 3 Patentee before: SUZHOU LIANKE NANO PURIFICATION TECHNOLOGY CO., LTD. |
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Address after: 231300 Lu'an, Shucheng, Hangzhou Port Economic Development Zone, Magnolia Road Patentee after: Shucheng Union Environmental Technology Co., Ltd. Address before: 231300 Lu'an, Shucheng, Hangzhou Port Economic Development Zone, Magnolia Road Patentee before: Shucheng joint surface treatment Co., Ltd. |
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Address after: 231300 Yulan Road, Hangbu Economic Development Zone, Shucheng County, Lu'an City, Anhui Province Patentee after: China Singapore United Technology (Anhui) Co.,Ltd. Address before: 231300 Yulan Road, Hangbu Economic Development Zone, Shucheng County, Lu'an City, Anhui Province Patentee before: SHUCHENG LINK ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |
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