A kind of radiation curable adhesive and preparation method thereof
Technical field
The present invention relates to radiation curing technology field and paint field, particularly UV radiation curable adhesive and preparation method thereof.
Background technology
The sixties in last century, Germany has released the green technology of first-generation UV coating, in the industrial Preliminary Applications that obtains of woodwork coating.Later on radiation curing technology progressively extends to paper, various plastics, metal, stone material by the single base material of timber, even the application of base materials such as cement products, fabric, leather is used.
Radiation curing (UV/EB curing) is actually a kind of and realizes that by means of energy exposure source (ultraviolet ray or electron beam) chemical formulation (coating, printing ink and tackiness agent) is converted into the solid-state course of processing by liquid state.Compare with traditional curing technology, radiation curing technology have environmental protection, energy-conservation, curing speed is fast, advantage such as easy and simple to handle, has obtained fast development in recent ten years.The uv radiation curing technology does not contain solvent usually, and surrounding environment non-volatility organism (VOC) is produced, and the epoch that adapted to " decontamination, protection environment " call, thereby radiation curing technology more and more is subject to people's attention.
Quantity of radiant energy such as radiation curable coating is in utilizing, shortwave (300-400 nanometer) UV light or EB cause the macromolecular material (resin) that contains active function groups and aggregate into the coating variety that insoluble molten solid is filmed.
The material of radiation curable coating is formed:
1. oligopolymer, also claim oligopolymer or oligomer, low viscosity contains the synthetic resins of active function groups, it is the basic framework in the UV coating, under the effect of ultraviolet photon, form the paint film with three-dimensional arrangement, and give the various characteristics of paint film, for example hardness, snappiness, sticking power, gloss, performance such as ageing-resistant.Comprise: acrylic acid epoxy resin, acrylic acid polyester resin, acrylic polyether resin, vinylformic acid Synolac, acrylated polyurethane resin, acrylic-amino resin, unsaturated polyester resin, Resins, epoxy etc.
2. reactive thinner, main effect are the solid ingredients in the dissolving U V coating, regulation system viscosity.Thinner in the UV coating is not the volatile organic solvent that general coating uses, but participates in the non-volatility solvent that the film-forming process has response capacity directly.Reactive thinner generally is that molecular weight is little and intramolecularly contains a class monomer of polymerizable functional group with regard to chemical structure, becomes the part of paint film after the film forming.Comprise: Acrylic Acid Monomer, styrene monomer.
3.UV the luminous energy initiator is the key components in the UV coating, its role is to transmit the energy of ultraviolet photon, the crosslinking polymerization of rapid trigger monomer and oligopolymer, the liquid-solid switching process of promotion system.According to triggering mechanism, light trigger can be divided into free radical and positively charged ion two major types.Comprise: st-yrax ethers, benzophenone derivates, benzil ketals, ketoamine mixture etc.
4. auxiliary agent for satisfying concrete service requirements, improving some complementary component that paint film property is added, comprising: defoamer, flow agent, stablizer, dispersion agent etc.
The initiator system that radiation curing technology is used according to its curing mechanism, mainly contains two kinds of free radical type curing system and cationic curing systems.
Curing system for free radical type is characterized in: curing speed is fast, and the initiator type of free radical type is also more, and is comparatively deep to its research, and correlation theory is comparatively ripe; Shortcoming is: the volumetric shrinkage during curing is bigger, cause producing in the glue-line after curing very big internal stress, had a strong impact on tackiness agent bonding to base material, and the curing system of free radical type, the oxygen inhibition phenomenon is more serious, the deep layer position can't be solidified, for those ultraviolet radiations less than the dead angle, then can not solidify fully.
For cationic curing system, its characteristics: volumetric shrinkage is little after solidifying, and can not produce very big internal stress, strong adhesion, and the problem that does not have oxygen inhibition in the solidification process, for darker position or ultraviolet radiation less than the position, can effectively be cured.Shortcoming is: the initiator type that this system can be selected for use is less, and people are also very shallow for the research of this system, and curing speed differs bigger than the initiator system of free radical type.
In recent years, at the different characteristics of free radical type initiator system and cationic initiator system, the composite of free radical type initiator system and cationic initiator system appearred.But in general, effect also is not desirable especially.Contraction when solidifying as system is still bigger, thereby has brought uncertain internal stress to exist, and this can play bad counter productive to the cementability of tackiness agent.And the weather resistance of this compound system neither be very desirable, find especially in actual applications, and bonding material, through the weather-proof after date in 1 to 2 year, strength degradation was bigger, even the appearance of the phenomenons such as infiltration of cracking, tomography, water occurred.
Summary of the invention
Technical barrier to be solved by this invention is: there are problems such as uncertain internal stress, poor durability in the tackiness agent at present existing radiation curing free radical/positively charged ion compound system; The invention provides a kind of radiation curing free radical type and the composite tackiness agent of cationic initiator system, show excellent bonding strength and weathering resistance (being primarily aimed at high low temperature, humidity), can be widely used in the bonding of glass, iron, stainless steel, aluminium, pottery, stone material etc., have good bonding intensity and weather resistance.
The preparation method of the radiation curable adhesive that the free radical type with good bonding intensity and weather resistance that the another technical barrier that will solve of the present invention is to provide above-mentioned and cationic initiator system are composite, the particularly preparation method of the acrylate superpolymer that wherein adds.
Technical barrier to be solved by this invention can be realized by following scheme:
A kind of radiation curable adhesive comprises (A) origoester acrylate, (B) reactive diluent, (C) epoxy compounds; (D) radical photoinitiator, (E) cationic photoinitiator, (F) dibasic alcohol, (G) each analog assistant; Its characteristics are, also comprise (H) acrylate superpolymer.
A kind of radiation curable adhesive, its characteristics are that described each component ratio is:
(A) origoester acrylate: 10wt% to 70wt%,
(B) reactive diluent: 10wt% to 40wt%,
(C) epoxy compounds: 5wt% to 50wt%,
(D) radical photoinitiator: 0.1wt% to 10wt%,
(E) cationic photoinitiator: 0.1wt% to 10wt%,
(F) dibasic alcohol: 0wt% to 40wt%,
(G) each analog assistant: 0wt% to 10wt%,
(H) acrylate superpolymer: 0.1wt% to 50wt%.
The present invention is by adding a kind of homemade acrylate superpolymer in the compound system of free radical type initiator system and cationic initiator system to, the final a kind of inierpeneirating network structure (IPN) that forms, it is mixed that each component reaches molecular level, and two-phase all is external phase.Produce Synergy between the two-phase in this IPN system, played a part to force containing.When curing reaction took place, by the segregation phase-splitting, this had certain compensation effect to the volumetric shrinkage that produces in the radiation curing process owing to the incompatible of acrylate superpolymer, thereby improved the sticking power to base material.Because reducing of internal stress also can effectively be alleviated the crackle that produces between glue-line and the substrate interface, thereby avoid medium, the especially intrusion of water has reduced the desorption on the interface, has improved durability of products, weathering resistance.
The preparation method of described acrylate superpolymer is as follows:
1. in container, add deionized water, account for mix monomer total mass 5~30% partially mixed monomer, account for mix monomer total mass 0.01~0.5% initiator, account for the emulsifying agent of mix monomer total mass 1~10%, add pH value conditioning agent conditioned reaction thing pH value to 7~8 again, after feeding nitrogen, pre-emulsification 15~35min heats up then and reacts;
2. after reaction proceeded to 0.5~3 hour, adding accounted for the residual monomer of mix monomer total mass 10~90%, and adds the emulsifying agent that accounts for mix monomer total mass 1~10%, continued reaction 1~4 hour;
3. with the emulsion that makes with after being the emulsion splitter breakdown of emulsion of 0.5~3 times of emulsion cumulative volume, obtain polymkeric substance washing for several times after, in 40 ℃~70 ℃ vacuum driers, dry 72 hours, obtain acrylic ester polymer.
The mix monomer of above-mentioned steps in 1. is: methyl acrylate (MA), ethyl propenoate (EA), butyl acrylate (BA), ethyl acrylate (EHA), vinylformic acid (AA), methacrylic acid (MMA), vinyl cyanide (AN), vinylformic acid methoxy ethyl ester (MEA), vinylformic acid ethoxy ethyl ester (EEA), glycidyl methacrylate (GMA), glycidyl allyl ether (AGE), 2-chloroethyl vinyl ether (CEVE), vinylchlorid vinyl acetate between to for plastic (VCA), two or more combination in the epoxy acetic ester (CCA).Preferably, described mix monomer is 80~150 parts of butyl acrylates, 70~160 parts of vinyl cyanide, 1~10 part of methyl methacrylate, 1~20 part of glycidyl methacrylate.
Above-mentioned steps 1. in used initiator be: the combination of one or more in Potassium Persulphate (KPS), ammonium persulphate (APS), hydrogen phosphide cumene (CHP), the tertbutyl peroxide (TBHP).
Above-mentioned steps 1. in, be warming up to 65 ℃~90 ℃ and react.
The emulsifying agent of above-mentioned steps in 2. is: one or more combinations in sodium lauryl sulphate (SDS), sodium laurylsulfonate or the Sodium dodecylbenzene sulfonate (SDBS).
The reaction of above-mentioned steps in 2. added residual monomer after 1.5 hours.
The above-mentioned steps 3. middle emulsion splitter that uses is: NaOH, Al
2(SO
4)
3, ethanol, NaCl, CaCl
2, FeSO
4, Fe
2(SO
4)
3, MgSO
4In one or more combination.
The pH value conditioning agent of described step in 2. can be sodium bicarbonate.
Described (A) origoester acrylate, its characteristics are, be bifunctional oligopolymer, polyfunctional group oligopolymer or its combination, for: the combination of one or more in epoxy acrylate oligomer, urethane acrylate oligomer, polyester acrylic ester oligomer, polyoxyalkylene acrylate ester oligomer, the acroleic acid esterification polyacrylic acid ester oligomer.
Described origoester acrylate, viscosity are 3000cps~50000cps (60 ℃), purchase in companies such as SARTOMER, ETERNAL.
Described (B) reactive diluent, its characteristics are, comprise vinyl reactive diluent and esters of acrylic acid reactive diluent.The reactive diluent of described radiation-hardenable can be used for adjusting the viscosity of tackiness agent, comprise at least one when be exposed under the ultraviolet radiation condition can crosslinking polymerization functional group as, vinyl, vinyl ether, propenyl etc.
Described vinyl-based thinner comprises: vinyl ethers, vinylbenzene and derivative thereof.Described vinyl ethers is: dodecyl vinyl, 2-ethylhexyl vinyl ether, 1,6-hexylene glycol divinyl ether; Described vinylbenzene and derivative thereof include but not limited to p-methylstyrene, 2,4,6-Three methyl Benzene ethene, to methoxy styrene, to tert.-butoxy vinylbenzene, to one or more the combination in chloro-styrene, the a-vinyl toluene.
Described esters of acrylic acid reactive diluent is: the combination of one or more in the thinner of simple function group, the thinner of bifunctional, trifunctional, the multi-functional thinner.
The thinner of described simple function group is: (the combination of one or more in β-CEA), 2-phenoxyethyl acrylate (PHEA), methyl acrylate (MA), methyl methacrylate (MMA), butyl acrylate (BA), the ethyl propenoate (EA) of methacrylic acid-beta-hydroxy ethyl ester (HEMA), isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA), β-propyloic acrylic ester.The thinner of described bifunctional is: the combination of one or more in 1,6 hexanediol diacrylate (HDDA), propylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), neopentylglycol diacrylate (NPGDA), the 2-hydroxyethyl methacrylic ester phosphoric acid ester (HEMAP).Described trifunctional or multi-functional thinner are: the combination of one or more in Viscoat 295 (TMPTA), pentaerythritol triacrylate (PETA), the dipentaerythritol acrylate (DPHA).
Described (C) epoxy compounds is: the Resins, epoxy of the Resins, epoxy of bisphenol A-type, Bisphenol F type, one or more the combination in the alicyclic radical epoxy compounds.
Described (D) radical photoinitiator comprises crack type photoinitiator and/or hydrogen-capture-type light initiator.
The light trigger of described cracking type is: a, a-dimethoxy-a-phenyl methyl phenyl ketone (DMPA, commodity are called the Irgacure651 light trigger) or a, a-diethoxy acetophenone (DEAP) or 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP, commodity are called Darocur1173) or 1-hydroxyl-cyclohexyl benzophenone (HCPK, commodity are called Irgacure184) or 2-phenyl-2,2-2 methylamino--1-(4-morpholinyl phenyl)-1-butanone (BDMB, commodity are called Irgacure369) or 2, the combination of one or more in 4, the 6-Three methyl Benzene formyl diphenyl phosphine oxide (TPO).
Described hydrogen-capture-type light initiator is: the combination of one or more in benzophenone (BP) or isopropyl thioxanthone (ITX) or 2, the 4-diethyl thioxanthone (DETX).
Described (E) cationic photoinitiator comprises salt compounded of iodine light trigger, sulfonium salt photoinitiator initiator, iron arene light trigger.
Described salt compounded of iodine light trigger comprises: 4,4 ' dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI820).
Described sulfonium salt photoinitiator initiator comprises: the triphenyl sulfosalt.
Described iron arene light trigger comprises: cyclopentadiene isopropyl benzene iron hexafluorophosphate (Irgacure261).
Described (F) dibasic alcohol is: ethylene glycol, glycol ether, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1, the combination of one or more in the 4-butyleneglycol.Alcohol be as chain-transfer agent and with the epoxy compounds copolymerization, to improve the speed of cationic curing system.
Described (G) each analog assistant comprises defoamer, adhesion promoter, flow agent.
A kind of preparation method of radiation curable adhesive comprises:
(1) preparation of acrylate superpolymer (H);
(2) with reactive diluent (B), acrylate superpolymer (H) combination of dibasic alcohol (F) and step (1) preparation, normal temperature stirred 48 hours for following 23 ℃;
(3) add origoester acrylate (A) and epoxy compounds (C) and continue to stir 6~10 hours, temperature is 35~40 ℃;
(4) be cooled to below 30 ℃, add each analog assistant of radical photoinitiator (D) cationic photoinitiator (E) (G), stirred 1 hour, with 50 microns net filtration dischargings.
The preparation of the acrylate superpolymer (H) in the described step (1) comprises the steps: 1. to add deionized water, partially mixed monomer, initiator, pH value conditioning agent in container, behind the feeding nitrogen, pre-emulsification 15~35min heats up then and reacts;
2. after reaction proceeds to 0.5~3 hour, add residual monomer and replenish a certain amount of emulsifying agent continuation reaction 1~4 hour;
3. after the emulsion that makes being used the emulsion splitter breakdown of emulsion, after the washing for several times of acquisition polymkeric substance, in 40 ℃~70 ℃ vacuum driers, dry 72 hours, obtain acrylic ester polymer.
The mix monomer of above-mentioned steps in 1. is: methyl acrylate (MA), ethyl propenoate (EA), butyl acrylate (BA), ethyl acrylate (EHA), vinylformic acid (AA), methacrylic acid (MMA), vinyl cyanide (AN), vinylformic acid methoxy ethyl ester (MEA), vinylformic acid ethoxy ethyl ester (EEA), glycidyl methacrylate (GMA), glycidyl allyl ether (AGE), 2-chloroethyl vinyl ether (CEVE), vinylchlorid vinyl acetate between to for plastic (VCA), the combination of one or more in the epoxy acetic ester (CCA).
Above-mentioned steps 1. in used initiator be: the combination of one or more in Potassium Persulphate (KPS), ammonium persulphate (APS), hydrogen phosphide cumene (CHP), the tertbutyl peroxide (TBHP).
Above-mentioned steps 1. in, be warming up to 65 ℃~90 ℃ and react.
The emulsifying agent of above-mentioned steps in 2. is: the combination of one or more in sodium lauryl sulphate (SDS), sodium laurylsulfonate or the Sodium dodecylbenzene sulfonate (SDBS).
Above-mentioned steps 2. middle reaction added residual monomer after 1.5 hours.
The above-mentioned steps 3. middle emulsion splitter that uses is: NaOH, A1
2(SO4)
3, ethanol, NaCl, CaCl
2, FeSO
4, Fe
2(SO4)
3, MgSO
4In one or more combination.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described.
Embodiment 1:
1.1 the preparation of esters of acrylic acid superpolymer,
Its method is:
A is in the four-hole boiling flask that agitator, thermometer, reflux exchanger and nitrogen feeding mouth are housed, add a certain amount of deionized water, partially mixed monomer (accounting for mix monomer total mass 20%), sodium bicarbonate, Sodium dodecylbenzene sulfonate (SDBS, account for mix monomer total mass 5%) and Potassium Persulphate (KPS accounts for mix monomer total mass 0.1%).After feeding nitrogen, earlier pre-emulsification 20min is warming up to 75 ℃ then and reacts;
B progressively adds the mix monomer (monomer is at the uniform velocity to drip mode, and the time is 3 hours) of residue 80% in the mode that drips, and adds Sodium dodecylbenzene sulfonate (accounting for mix monomer total mass 2%) after reaction is carried out 1.5 hours, continues reaction 2 hours;
C with isopyknic 2%NaCl solution breakdown of emulsion, and with after the deionized water washing 4 times, places 60 ℃ of vacuum drying ovens with the emulsion that makes, and dry the placement 72 hours gets the acrylate superpolymer.
Annotate: in the mix monomer, 100 parts of butyl acrylates (BA), 100 parts of vinyl cyanide (AN), 2 parts of methyl methacrylates (MMA), 4 parts of glycidyl methacrylate (GMA).
1.2 the component of tackiness agent and preparation
The tackiness agent component:
(A) urethane acrylate and epoxy acrylate compound 48.5%
(B) reactive diluent 20.5%
Butyl acrylate (4 parts), isobornyl acrylate (3.5 parts), hexylene glycol divinyl ether (1.5 parts)
(C) Resins, epoxy (E51) 18%
(D) radical photoinitiator 1.8%
(1173∶184∶TPO=1.0∶0.8∶1.3)
(E) cationic photoinitiator (IHT-PI820) 1.0%
(F) ethylene glycol 3.0%
(G) each analog assistant 2.0%
(H) the acrylate superpolymer 5.2%
1.3 tackiness agent preparation:
With (B) (H) (F) three components mixing, (23 ℃) stirred 48 hours under the normal temperature earlier; Add (A) then and (C) continue stirring 8 hours, temperature is 35~40 ℃; Be cooled to below 30 ℃, add (D) (E) (G), stirred l hour, with 50 microns net filtration dischargings.
1.4 tackiness agent performance
Shearing resistance: 28MPa
Torsional strenght: 38Nm
High low temperature cycles test (low temperature-40 ℃, 85 ℃ of high temperature, 85%RH): slightly grow dim
Embodiment 2:
2.1 the preparation method of acrylate superpolymer is with embodiment 1
2.2 the component of tackiness agent and preparation
The tackiness agent component:
(A) urethane acrylate and epoxy acrylate compound 46%
(B) mix monomer 20.5%
Butyl acrylate (4 parts), isobornyl acrylate (3.5 parts), hexylene glycol divinyl ether (1.5 parts)
(C) Resins, epoxy (E51) 19%
(D) radical photoinitiator 1.8%
(1173∶184∶TPO=1.0∶0.8∶1.3)
(E) cationic photoinitiator (IHT-PI820) 1.0%
(F) ethylene glycol 3.0%
(G) each analog assistant 2.0%
(H) the acrylate superpolymer 6.7%
2.3 the tackiness agent preparation: the compound method of tackiness agent is with embodiment 1
2.4 tackiness agent performance
Shearing resistance: 30MPa
Torsional strenght: 43Nm
High low temperature cycles test (low temperature-40 ℃, 85 ℃ of high temperature, 85%RH): do not grow dim substantially
Embodiment 3:
3.1 the preparation method of acrylate superpolymer is with embodiment 1
3.2 the component of tackiness agent and preparation
The tackiness agent component:
(A) urethane acrylate and epoxy acrylate compound 46%
(B) mix monomer 20.5%
Butyl acrylate (4 parts), isobornyl acrylate (3.5 parts), hexylene glycol divinyl ether (1.5 parts)
(C) Resins, epoxy (E51) 17%
(D) radical photoinitiator 1.8%
(1173∶184∶TPO=1.0∶0.8∶1.3)
(E) cationic photoinitiator (IHT-PI820) 1.0%
(F) ethylene glycol 3.0%
(G) each analog assistant 2.0%
(H) the acrylate superpolymer 9.7%
3.3 the tackiness agent preparation: the compound method of tackiness agent is with embodiment 1
3.4 tackiness agent performance
Shearing resistance: 27MPa
Torsional strenght: 35Nm
High low temperature cycles test (low temperature-40 ℃, 85 ℃ of high temperature, 85%RH): do not grow dim
Embodiment 4:
4.1 the preparation method of acrylate superpolymer is with embodiment 1
4.2 the component of tackiness agent and preparation
The tackiness agent component:
(A) urethane acrylate and epoxy acrylate compound 48.5%
(B) mix monomer 20.5%
β-propyloic acrylic ester (6 parts), 1,6 hexanediol diacrylate (3 parts), 2-ethylhexyl vinyl ether (1.5 parts)
(C) Resins, epoxy (E51) 18%
(D) radical photoinitiator 1.8%
(1173∶184∶TPO=1.0∶0.8∶1.3)
(E) cationic photoinitiator (IHT-PI820) 1.0%
(F) ethylene glycol 3.0%
(G) each analog assistant 2.0%
(H) the acrylate superpolymer 5.2%
4.3 the tackiness agent preparation: the compound method of tackiness agent is with embodiment 1
4.4 tackiness agent performance
Shearing resistance: 31MPa
Torsional strenght: 45Nm
High low temperature cycles test (low temperature-40 ℃, 85 ℃ of high temperature, 85%RH): grow dim
Embodiment 5:
5.1 the preparation method of acrylate superpolymer is with embodiment 1
5.2 the component of tackiness agent and preparation
The tackiness agent component:
(A) urethane acrylate and epoxy acrylate compound 47%
(B) mix monomer 22.7%
β-propyloic acrylic ester (6 parts), 1,6 hexanediol diacrylate (3 parts), 2-ethylhexyl vinyl ether (1.5 parts)
(C) Resins, epoxy (E51) 16%
(D) radical photoinitiator 1.8%
(1173∶184∶TPO=1.0∶0.8∶1.3)
(E) cationic photoinitiator (IHT-PI820) 1.0%
(F) ethylene glycol 3.0%
(G) each analog assistant 2.0%
(H) the acrylate superpolymer 6.5%
5.3 the tackiness agent preparation: the compound method of tackiness agent is with embodiment 1
5.4 tackiness agent performance
Shearing resistance: 29MPa
Torsional strenght: 44Nm
High low temperature cycles test (low temperature-40 ℃, 85 ℃ of high temperature, 85%RH): do not grow dim substantially
Above content shows and has described ultimate principle of the present invention, principal character and advantage of the present invention.The personnel of the industry should understand; the present invention is not subjected to the restriction of above-mentioned example; that describes in above-mentioned example and the explanation just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all will fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.