CN102660205B - 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 PDF

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CN102660205B
CN102660205B CN 201210178296 CN201210178296A CN102660205B CN 102660205 B CN102660205 B CN 102660205B CN 201210178296 CN201210178296 CN 201210178296 CN 201210178296 A CN201210178296 A CN 201210178296A CN 102660205 B CN102660205 B CN 102660205B
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hot melt
melt adhesive
acrylate
composition
copolyesters
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CN102660205A (en
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任耀彬
刘学习
张立伟
吴文明
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China Singapore United Technology Anhui Co ltd
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SUZHOU LINK SYN-MATERIALS Co Ltd
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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

The preparation method of acrylic esters hot-melt glue composition and the crosslinked hot melt adhesive of UV
Technical field
The invention belongs to the hot melt adhesive technical field, be specifically related to a kind of preparation method of composition and UV cross linked acrylic hot melt adhesive of acrylic esters hot-melt glue.
Background technology
Hot melt adhesive (Hot Melt Adhesive) is a kind of multicomponent mixture take thermoplastics as matrix, it is applied to substrate surface with melt form and carries out bonding, it is solid-state at normal temperatures, be fused into liquid state after the heating, the coating, wetting bonded after, through pressing cooling, within 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 manufacture line operational requirement, can be applied on the high-speed and continuous production line again.
At present, the main body in hot melt adhesive market is 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 developed, 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, easily synthetic, good endurance, low-temperature performance is good, the transparency is good, basically when nontoxic and non-environmental-pollution, manufacturing and storing without fire hazard, bonding wide, the characteristics such as adhesiveproperties is good.Yet polyacrylic ester is both non-crystallizable, also unlike traditional hot-melt adhesive larger cohesive strength is arranged when cooling off, the defectives such as glue that acrylic esters hot-melt glue is inadequate because of its crosslinking degree at present, Joint strength is low, temperature tolerance is poor and high temperature hot pressing easily overflows are applied difficulty in electron trade.
Summary of the invention
The object 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 composition 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 achieving the above object, the present invention adopts two technical schemes, these two schemes comprise the technical identical specified features that is mutually related---and the composition that forms UV cross linked acrylic hot melt adhesive consists of, therefore two technical schemes belong to a total inventive concept, meet the unicity requirement.
In order to realize first purpose, the technical solution used in the present invention is: the composition of acrylic esters hot-melt glue is characterized in that: said composition comprises the component of following mass content ratio: acrylate copolymer 9-90%, copolyesters 9-90%, oxidation inhibitor 0.1-1%, initiator 0.1-1%; The weight-average molecular weight of acrylate copolymer 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 composition of aforesaid acrylic esters hot-melt glue, described acrylate copolymer contains the component of following mass percent: structural unit glycidyl methacrylate 1-10%; Contain vinyl group or methacrylate based group to benzophenone 0.5-5%; Also comprise one or more of following structural unit, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl acrylate, ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer in the structural unit of multipolymer.
The composition 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-diethyl-1,5-PD (DEPD) 5-30%, dimer diols 5-50%.
The composition of aforesaid acrylic esters hot-melt glue, the second-order transition temperature of described 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 composition 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, 2,6-ditertbutylparacresol, 4,4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol) one or more.
For realizing second purpose, the technical solution adopted in the present invention is: the preparation method of UV cross linked acrylic hot melt adhesive comprises following concrete steps: acrylate copolymer and copolyesters synthetic respectively; The composition of acrylate copolymer and copolyesters formation is added twin screw extruder high-speed mixing, 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 high-speed mixing, coating, ultraviolet light cross-linking, rolling step are carried out on transmission mechanism continuously, and described ultraviolet light cross-linking step is finished by UV lamp, UV Measurement and Control System.
Beneficial effect of the present invention: it is crosslinked that the present invention adopts the crosslinked hot melt colloid molecule (in the molecule or intermolecular) that makes of UV after hot melt adhesive coating, improved the internal cohesive energy of hot melt colloid to improve crosslinking degree, hot melt adhesive of the present invention also adds the dimer acid type copolyesters of a great deal of except matrix resin simultaneously, the introducing of dimer acid type copolyesters can obtain excellent adhesive property, 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 preparation 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
The invention will be further described below in conjunction with the drawings and specific embodiments: 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.
It is worth mentioning that, the used whole reagent raw materials of the present invention, the monomer, the monomer of copolyesters, oxidation inhibitor, the initiator that comprise acrylate copolymer can independently synthesize by the purchase of commercialization approach or by buying the relevant monomer raw material, synthetic technical matters is known by those skilled in the art, therefore is not described in detail.In addition, the present invention's related technology (high-speed mixing, situ-formed graft, increase-volume chain extension, heat seeling coating etc.) in the hot melt adhesive preparation process is those skilled in the art to be known, and therefore is not described in detail.
The composition of acrylic esters hot-melt glue is characterized in that, said composition comprises the component of following mass content ratio: acrylate copolymer 10-90%, copolyesters 10-90%, oxidation inhibitor 0.1-1%, light trigger 0.1-1%; The weight-average molecular weight of acrylate copolymer 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, 2,6-ditertbutylparacresol, 4,4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol) one or more, 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 the various initiators such as benzophenone, energy transfer initiator such as thioxanthone, ionic reaction type initiator such as diaryl group iodized salt, is used for crosslinked under the UV irradiation of auxiliary heat melten gel molecule.
The preparation method of UV cross linked acrylic hot melt adhesive, it is characterized in that: the method will cause with UV-light acrylate copolymer and the composite hot-melt adhesive composition that obtains of copolyesters of functional group, and said composition makes partial cross-linked hot melt adhesive through UV-crosslinked again through heat seeling coating.
Structural unit glycidyl methacrylate 1-10% in the acrylate copolymer, optimum proportion is 3-5%; Contain vinyl group or (methyl) acrylate group to benzophenone 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 by phenol oxygen key; Other copolymerization structural unit of acrylate copolymer also comprises one or more in the following monomer, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate and (methyl) Isooctyl acrylate monomer.More than be weight percentage.
Cause the preparation process of the acrylate copolymer of functional group below in conjunction with what embodiment 1-4 explanation contained initiator with UV-light.
Embodiment 1
(epoxide group is used for carrying out chain extending reaction with the carboxyl of copolyesters to get by weight percentage 3 parts of 42 parts of ethyl propenoates, 49 parts of butyl acrylates, glycidyl methacrylate, reduce simultaneously the hydrolysis of copolyesters), 0.5 part of 1 part of 4-vinyl-4-methoxy benzophenone (the UV initiating group produces free 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 thermometer, reflux condensing tube, agitator and nitrogen conduit temperature; system under nitrogen protection 62 ℃ carried out copolymerization 6 hours, then 76 ℃ of lower copolymerization 8 hours, obtain the acrylate copolymer solution of 40% solids content.Then, under the lucifuge condition copolymer solution is painted the 0.150mm thick coating with scraper, then dry out solvent and residual monomer obtain copolymer adhesive film under the lucifuge condition.The weight-average molecular weight that records this acrylate copolymer 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 glycidyl methacrylate is that the weight content of 3%, 4-vinyl-4-methoxy benzophenone is 1%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.5%.
Embodiment 2
Get by weight percentage 0.4 part of 42 parts of ethyl propenoates, 47 parts of butyl acrylates, 3 parts of glycidyl methacrylate, 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.Adopt the technique of embodiment 1 to make copolymer adhesive film.The weight-average molecular weight that records this acrylate copolymer 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 glycidyl methacrylate is that the weight content of 3%, 4-vinyl-4-methoxy benzophenone is 3%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.4%.
Embodiment 3
Get by weight percentage 0.4 part of 20 parts of β-dimethyl-aminoethylmethacrylates, 43 parts of butyl methacrylate, 3 parts of glycidyl methacrylate, 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.Adopt the technique of embodiment 1 to make copolymer adhesive film.The weight-average molecular weight that records this acrylate copolymer 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 glycidyl methacrylate is that the weight content of 3%, 4-vinyl-4-methoxy benzophenone is 3%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.4%.
Embodiment 4
Get by weight percentage 0.4 part of 20 parts of β-dimethyl-aminoethylmethacrylates, 44 parts of butyl acrylates, 3 parts of glycidyl methacrylate, 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.Adopt the technique of embodiment 1 to make copolymer adhesive film.The weight-average molecular weight that records this acrylate copolymer 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 glycidyl methacrylate is that the weight content of 3%, 4-vinyl-4-methoxy benzophenone is 3%, and the weight content of initiator Diisopropyl azodicarboxylate is 0.4%.
Copolyesters contains structural unit dimeracid (such as the vegetable oil acid dimer), and mass percent is 10-50%, and optimum proportion is 10-25%; The structural unit that copolyesters contains dibasic alcohol is 2,4-diethyl-1,5-PD (DEPD), and mass percent is 5-30%, and 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 may contain 1,6-hexylene glycol, 2,4-diethyl-1,5-PD.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.
Example 5
Dibasic alcohol: 14.3 moles of butyleneglycols, 11.44 moles of 5.72 moles of 1,6-hexylene glycols and 2,4-diethyl-1,5-PDs (DEPD).Diprotic acid raw material: 9.91 moles of 15.56 moles of dimethyl terephthalate (DMT), 2.83 moles of vegetable oil acid dimers and 1,6-hexanodioic acids.The esterifying catalyst and the 10 gram oxidation inhibitor that add in addition 3 grams.The reaction kettle of the esterification that first dibasic alcohol is added 10L, reactor is equipped with thermometer, reflux condensing tube, agitator 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, until distill in the sundries without till the 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 reactor is less than 1mbar.The reaction product that takes a morsel is painted the 0.150mm thick coating 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%.
Example 6
Dibasic alcohol: 11.3 moles of butyleneglycols, 14.44 moles of 5.72 moles of 1,6-hexylene glycols and 2,4-diethyl-1,5-PDs (DEPD).Diprotic acid raw material: 9.91 moles of 15.56 moles of dimethyl terephthalate (DMT), 2.83 moles of vegetable oil acid dimers and 1,6-hexanodioic acids.The esterifying catalyst and the 10 gram thermo-stabilizers that add in addition 3 grams.Preparation technology is with example 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%.
Example 7
Dibasic alcohol: 11.3 moles of butyleneglycols, 14.44 moles of 5.72 moles of 1,6-hexylene glycols and 2,4-diethyl-1,5-PDs (DEPD).Diprotic acid raw material: 9.91 moles of 12 moles of dimethyl terephthalate (DMT), 6.39 moles of vegetable oil acid dimers and 1,6-hexanodioic acids.The esterifying catalyst and the 10 gram thermo-stabilizers that add in addition 3 grams.Preparation technology is with example 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%.
Example 8
Dibasic alcohol: 11.3 moles of butyleneglycols, 14.44 moles of 5.72 moles of 1,6-hexylene glycols and 2,4-diethyl-1,5-PDs (DEPD).Diprotic acid raw material: 6.35 moles of 15.56 moles of dimethyl terephthalate (DMT), 6.39 moles of vegetable oil acid dimers and 1,6-hexanodioic acids.The esterifying catalyst and the 10 gram thermo-stabilizers that add in addition 3 grams.Preparation technology is with example 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 composition of acrylate copolymer and copolyesters formation is added twin screw extruder high-speed mixing, 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 ℃.High-speed mixing, coating, ultraviolet light cross-linking, rolling step are carried out on transmission mechanism continuously, and described ultraviolet light cross-linking step is finished 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 easily overflows in the poor heat resistance, bonding process, after composition of the present invention is made the hot melt adhesive coating, under UV-light (UV), on the acrylate copolymer molecular side chain to the benzophenone group activation, capture the hydrogen atom of tertiary carbon atom on this high-polymer molecular chain, the carbonyl carbon atom is combined with the carbon atom that hydrogen atom links to each other simultaneously, Formed carbon saturated bond and hydroxyl, and crosslinking reaction is finished.By regulating the concentration of p-Xylol ketone in the acrylate copolymer, can control the degree of crosslinking of final hot melt adhesive film.The crosslinked hot melt colloid molecule (molecule is interior or intermolecular) that makes is partial cross-linked, improved the internal cohesive energy of hot melt colloid, improved initial bonding strength, hot melt adhesive of the present invention also adds the dimer acid type copolyesters of a great deal of except matrix resin simultaneously, it is good that the introducing of dimer acid type copolyesters can obtain excellent adhesive property, resistance, and the introducing of dimer acid type copolyesters can obtain higher thermotolerance, good weather-proof, water tolerance and elasticity.
Above-mentioned composition comprises acrylate copolymer, copolyesters, oxidation inhibitor, initiator, described composition is added the twin screw extruder high-speed mixing situ-formed graft, increase-volume chain extending reaction occur simultaneously, grafting, chain extending reaction occur between the hydroxyl, carboxyl of acrylate copolymer epoxy group(ing) and copolyesters, copolyesters also connects together by acrylate copolymer each other, obtains the hot melt colloid; Hot melt adhesive enters the hot melt adhesive trunnion with heating function by volume pump; The melt viscosity of composition 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, feeds 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 finished 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 by dispense tip 2, make it be adhered to substrate surface, again by continuously coating of transmission mechanism (comprising rolling-up mechanism 3), simultaneously 4 irradiations of UV lamp scribble the base material of hot melt adhesive in the cross-linking process, under the assistance of light trigger in the molecule crosslinked 6(molecule of colloid or intermolecular), improve the hot melt adhesive internal cohesive energy.
Preparation process below by embodiment 9-14 UV cross linked acrylic of the present invention hot melt adhesive.
Embodiment 9
Get embodiment 1 with acrylate copolymer 2000 grams of UV-light initiating group and chain extension group, other gets copolyesters 3000 grams of embodiment 5 preparations, respectively after the lucifuge melting, above-mentioned composition is added twin screw extruder (length-to-diameter ratio of forcing machine is 52, and temperature is 180~150 ℃) carry out high-speed mixing, grafting and chain extension.In this process, the epoxy group(ing) in the acrylate copolymer 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 composition, were conducive to be coated with into the glued membrane of different thickness.Then, hot melt adhesive enters the hot melt adhesive trunnion with heating function by volume pump.Then with the composition 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.Shearing temperature tolerance and the stripping strength of hot melt adhesive film see Table 1.Wherein, the weight content of acrylate copolymer (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 example 2 acrylate copolymers 2000 gram, other gets example 6 copolyesters 3000 grams, prepares hot melt adhesive film according to the technique of embodiment 9.Shearing temperature tolerance and the stripping strength of hot melt adhesive film see Table 1.Wherein, the weight content of acrylate copolymer (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 example 2 acrylate copolymers 3000 gram, other gets example 6 copolyesters 3000 grams, prepares hot melt adhesive film according to the technique of example 9.Shearing temperature tolerance and the stripping strength of hot melt adhesive film see Table 1.Wherein, the weight content of acrylate copolymer (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 example 3 acrylate copolymers 2000 gram, other gets example 7 copolyesters 3000 grams, prepares hot melt adhesive film according to the technique of example 9.Shearing temperature tolerance and the stripping strength of hot melt adhesive film see Table 1.Wherein, the weight content of acrylate copolymer (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 example 3 acrylate copolymers 2000 gram, other gets example 8 copolyesters 3000 grams, prepares hot melt adhesive film according to the technique of example 9.Shearing temperature tolerance and the stripping strength of hot melt adhesive film see Table 1.Wherein, the weight content of acrylate copolymer (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 example 4 acrylate copolymers 2000 gram, other gets example 8 copolyesters 3000 grams, prepares hot melt adhesive film according to the technique of example 9.Shearing temperature tolerance and the stripping strength of hot melt adhesive film see Table 1.Wherein, the weight content of acrylate copolymer (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 following describes performance test process and the result of UV cross linked acrylic hot melt adhesive, as shown in table 1.
Testing method
The molecular weight of acrylate copolymer and copolyesters adopts gel permeation chromatography, GPC, analyzing molecules amount and distribution thereof.Analytical instrument, Symyx Rapid GPC; Solvent, tetrahydrofuran (THF), concentration is 1 mg/ml; The sample taken amount, 0.25 milliliter; Kapillary nitrogen flow rate 1.8 mark condition liter/min clocks.
The melt viscosity of acrylate copolymer, 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 acrylate copolymer 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 sample preparation of commodity polyester hot-melt adhesive glue is with making hot melt adhesive blade coating device, Ge Laxin separate-type paper (grammes per square metre, 80g/ ㎡ by oneself; 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 temperature tolerance (shear adhesion failure temperature, SAFT) according to ASTM D4498 standard testing.Size of sample, 25mm * 25mm; Load, 500g; Heat-up rate, 0.5 ℃/min.Record sample corresponding temperature value when coming off, the thermotolerance of hot melt adhesive film are with this temperature value sign, and test result sees 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 sees 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
Figure BDA00001716280500151
According to table 1, the content of light-initiated functional group raise can the Effective Raise hot melt adhesive cohesive strength; 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.
Above-described embodiment does not limit the present invention in any form, and all employings are equal to replaces or technical scheme that the mode of equivalent transformation obtains, all drops on protection scope of the present invention.

Claims (7)

1. the composition of acrylic esters hot-melt glue, it is characterized in that: said composition comprises the component of following mass content ratio: acrylate copolymer 9-90%, copolyesters 9-90%, oxidation inhibitor 0.1-1%, initiator 0.1-1%; The weight-average molecular weight of acrylate copolymer is 50000~300000 g/mol, and second-order transition temperature is not higher than 20 ℃, and melt viscosity is 10-70Pa.S in the time of 160 ℃; Described copolyesters contains the structural unit of following mass percent: the dimer 10-50%, 2 of polyunsaturated vegetable oil acid, 4-diethyl-1,5-PD (DEPD) 5-30%, dimer diols 5-50%; Described acrylate copolymer contains the component of following mass percent: structural unit glycidyl methacrylate 1-10%; Contain vinyl group or methacrylate based group to benzophenone 0.5-5%; Also comprise one or more of following structural unit, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl acrylate, ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer in the structural unit of multipolymer.
2. the composition of acrylic esters hot-melt glue according to claim 1, it is characterized in that: the second-order transition temperature of described 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 ℃.
3. the composition 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, 2,6-ditertbutylparacresol, 4,4'-thiobis (the 6-tertiary butyl-3-(methyl) phenol) one or more.
4.UV the preparation method of cross linked acrylic hot melt adhesive is characterized in that: the method makes partial cross-linked hot melt adhesive through UV-crosslinked again with the described composition heat seeling coating of claim 1-4 any one.
5. the preparation method of UV cross linked acrylic hot melt adhesive according to claim 4 is characterized in that: comprise following concrete steps: acrylate copolymer and copolyesters synthetic respectively; The composition of acrylate copolymer and copolyesters formation is added twin screw extruder high-speed mixing, situ-formed graft, increase-volume chain extension, and at 130 ℃ of-160 ℃ of heat seeling coating base materials, ultraviolet light cross-linking, rolling packing.
6. the preparation method of UV cross linked acrylic hot melt adhesive according to claim 5, it 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 ℃.
7. the preparation method of UV cross linked acrylic hot melt adhesive according to claim 5, it is characterized in that: described high-speed mixing, coating, ultraviolet light cross-linking, rolling step are carried out on transmission mechanism continuously, and described ultraviolet light cross-linking step is finished by UV lamp, UV Measurement and Control System.
CN 201210178296 2012-06-01 2012-06-01 Acrylate hot melt adhesive composition and preparation method of hot melt adhesive by UV (ultraviolet) crosslinking Expired - Fee Related CN102660205B (en)

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