CN1394928A - Preparation method of UV-light solidified pressure-sensitive adhesive - Google Patents
Preparation method of UV-light solidified pressure-sensitive adhesive Download PDFInfo
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- CN1394928A CN1394928A CN 01120215 CN01120215A CN1394928A CN 1394928 A CN1394928 A CN 1394928A CN 01120215 CN01120215 CN 01120215 CN 01120215 A CN01120215 A CN 01120215A CN 1394928 A CN1394928 A CN 1394928A
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- acrylate
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 150000003254 radicals Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical group C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 2
- -1 hexyl amine bromides Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 2
- 238000003847 radiation curing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000005855 radiation Effects 0.000 description 9
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LZMCSJDPFPNZNL-UHFFFAOYSA-N benzene hexan-2-one Chemical class CC(CCCC)=O.C1=CC=CC=C1 LZMCSJDPFPNZNL-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a method for implementing safe and stable industrial preparation of acrylic pressure-sensitive adhesive which has no need of heating and drying, can be quickly cross-linked and solidified under the irradiation of UV light at normal temp. and can be made up using general coating machine. Said invention does not adopt water of general organic solvent, and has no any harmful volatile component, so that it is an environment-protecting type pressure-sensitive adhesive.
Description
Technical field:
The present invention relates to a kind of preparation method of UV-light solidified pressure-sensitive adhesive, particularly a kind of preparation method of pressure-sensitive adhesive of esters of acrylic acid of ultraviolet light polymerization.
Background technology:
Acrylic Pressure Sensitive Adhesive has been widely used in packing and the label industry.Generally, emulsion or solution polymerization process are adopted in the preparation of this tackiness agent.All there is shortcoming in the manufacture method of both of these case, if adopt solution polymerization process, so, employed solvent must be removed, normally dry under a comparatively high temps, a large amount of solvents that volatilize can bring great environmental pollution, and have increased industrial manufacturing cost; Adopt method of emulsion polymerization in solidifying the exsiccant process, to remove moisture, this need expend a large amount of energy, simultaneously, owing to adopted emulsifying agent, remaining in emulsifying agent in the tackiness agent can greatly influence the water resistance of emulsion pressure-sensitive adhesive, and damage otherwise performance, and as the transparency, adhesion etc.
Therefore, seek a kind of environmental friendliness and again the pressure-sensitive adhesive production technology of superior performance be an important developing direction, and had some to adopt electron radiations or ultraviolet light polymerization to prepare the example of pressure sensitive adhesive.
For example, Brockman etc. propose multi-functional acrylate's monomer and common acrylate monomer are mixed in U.S. Pat P 3,661,618, at room temperature coat on the base material, use high-energy radiation solidification again.Because need to use valuable electron radiation protector in this invention, cost is quite high, is difficult to industrialization.
U.S. Pat P 4181.752 adopts the prepolymerized method of ultraviolet radiation, earlier prepolymerization is to certain viscosity under the condition of control with monomer, and transformation efficiency is about about 10%, is applied to the further crosslinking curing of base material again, can reach 95% monomer conversion, system and have good adhesion property.Similarly method is also at U.S. Pat P 5183833, and USP 4943461, mention in USP 4223067 grades.
Karim adopts paracril as the polymkeric substance that increases the system viscosity in UV-light solidified pressure-sensitive.Except that the monomer of general acrylate, also introduce the polymerizable allylic cpd contain N in the diluting monomer, the photosensitive pressure sensitive adhesive of gained also has the good performance of sticking for vinyl plastics except that being suitable for the cohering of general material.
Yet, although above-mentioned several method can obtain effect in very a spot of experimental phase, if be amplified to the industrial production one-level many difficulties that can't overcome are just arranged, such as light pre-polymerization monomer methods, need to see through the reactor of UV-light, the resistance that must get rid of oxygen is poly-, and requires controlled polymerization process at any time, and these are to be difficult to obtain to realize in industrialized production.When adopting electron beam curing, the excess energy that electron radiation produces is usually burnt substrates coated, influences the quality of product.
Summary of the invention:
The invention provides a kind of preparation method who can safety and stability realizes the UV-light solidified pressure-sensitive adhesive of industrialized esters of acrylic acid.This pressure sensitive adhesive can be realized normal temperature coating on general coating machine, it can carry out industrial mass production easily, and the pressure-sensitive adhesive after the coating need not heat drying, normal temperature down just can be under the ultraviolet lamp radiation quick crosslinking curing, save energy greatly.
Specifically, the present invention prepares performed polymer with the mixture of acrylate monomer is implemented thermopolymerization under the mass polymerization state method, add the free radical chain transfer agent simultaneously, because the backflow effect of a small amount of solvent, make the partially polymerized heat in this polymerization-filling process obtain to discharge, thereby avoided the generation of implode.Simultaneously the molecular weight and the consumption of available adjustment chain-transfer agent and solvent that distributes also thereof are controlled.The diluted monomer dilution of institute's performed polymer that obtains back adds photosensitizers and mixes, but just can obtain the normal temperature coating and quick-setting pressure-sensitive adhesive under ultraviolet lamp.Perhaps with performed polymer and specific function monomer reaction, obtain the performed polymer of functionalization, coating back direct ultraviolet photo-crosslinking solidifies at normal temperatures, by the molecular weight of control prepolymer and the consumption of function monomer, can obtain the pressure-sensitive adhesive of various performances.
The preparation method of a kind of UV-light solidified pressure-sensitive adhesive of the present invention, in weight part, carry out according to the following steps successively: the preparation of (1) performed polymer is with soft monomer 40-90% (weight percent)
Hard monomer 5-45% (weight percent)
Function monomer 2-15% (weight percent)
Be mixed into 100 parts acrylate monomer blend; get wherein 30-50 part with after the benzoyl peroxide of 5-40 part solvent and 1-5 part mixes; join in the reactor; the free radical chain transfer agent stirring heating backflow of adding 0.1-1.5 part 5-20 minute; drip remaining acrylate monomer blend; after dripping off in 1-4 hour, back flow reaction 0.5-1.5 hour again, be performed polymer after the cooling.
Described soft monomer is the alkyl alcohol acrylate that contains 4-20 carbon atom, and they constitute the soft segment in the polymer chain, easily to being soaked into by maxxaedium.Commonly used has: n-butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate etc.
Described hard monomer is: methyl acrylate (MA), methyl methacrylate (MMA), vinyl-acetic ester (VAc), vinylbenzene (St), acrylonitrile (AN), Jia Jibingxisuanyizhi (EMA) or n-BMA (BMA) etc., their second-order transition temperature is higher, can be tackiness agent enough cohesive strengths are provided.
Described function monomer is: vinylformic acid, toxilic acid or maleic anhydride, (methyl) acrylamide, (methyl) propenoic acid beta-hydroxy ethyl ester or (methyl) propenoic acid beta-hydroxy propyl ester, (methyl) acrylic acid epoxy propyl ester, N hydroxymethyl acrylamide, methylene-succinic acid, multicondensed ethylene glycol double methyl methacrylate, Vinylstyrene etc.The introducing of function monomer can make the stripping strength of tackiness agent and hold viscosity and can be improved.Introduce polar group and can strengthen the sticking power of tackiness agent for polar surfaces, that introduces that crosslinked group then can obviously improve tackiness agent holds the viscosity energy.
Described free radical chain transfer agent is mainly used to the molecular weight and the distribution of controlling polymers, and then control performed polymer mass polymerization viscosity, mainly contains: n-dodecyl mercaptan, uncle's lauryl mercaptan or the like.
Described solvent is that strong free radical chain transferance tetracol phenixin, dimethylbenzene, ethanol, anhydrous methanol, Virahol or its mixture are arranged.
The present invention holds the viscosity energy for what improve polymkeric substance, glytidyl methacrylate copolymerization copolymerization is incorporated into performed polymer after, carry out acrylated.React as follows:
After being with active pair of key on the macromolecular chain of performed polymer, can be effectively caused by light trigger crosslinked, thereby improve the cohesive strength and the curing speed of tackiness agent greatly, obtain ideal and hold sticking intensity.
Concrete scheme is as follows: can further add 0.1-1 part four hexyl amine bromides in performed polymer more than 100 parts and make catalyzer, be heated to 110-115 ℃ of vinylformic acid that slowly splashes into 1-15 part, drip off the back and continue reaction 0.5-2 hour, can obtain acrylated performed polymer.(2) preparation of pressure sensitive adhesive
Acrylate with 5-100 part is done monomer diluent, adds light trigger and light-initiated auxiliary agent and mixes, and the light trigger consumption is generally 1-5 part, and light-initiated auxiliary dosage is generally 1-5 part.Add 100 parts of performed polymers again, the system viscosity of making maintains the 1000-5000 centipoise.Evenly be applied on the matrix,, place and press radiation curing under the ultra-violet lamp as polyester (PET) film.
In order to improve photopolymerization or crosslinked efficient, select suitable light trigger particularly important.Generally the UV-light light trigger of energy initiating polymerization of vinyl monomer can be used.Ultraviolet initiator commonly used is divided into two kinds: a kind of is free radical type; Another kind is cationic.Wherein the light trigger purposes of free radical type is the most extensive, and commonly used have st-yrax class ether as benzoin methyl ether, Benzoin ethyl ether, st-yrax n-butyl ether etc.; Benzene hexanone class is as benzophenone, D-1173 (Ciba) etc.In order to overcome the surperficial inhibition of oxygen, also to add organic amine as light-initiated auxiliary agent, as triethylamine, diethylamine, diethanolamine, trolamine or the like all are good selections.
The 750W medium pressure mercury lamp that the ultra-violet curing light source can adopt the Beijing Electrooptic Source Inst to produce.Effectively optical radiation centre wavelength is at 365 nanometers, radiation power 4.5mw/cm
2
Testing method is as follows: the mensuration of (1) 180 ° of stripping strength
With wide be that 25 centimetres Pressuresensitive Tape evenly is affixed on the stainless steel plate under certain pressure, after under temperature is 23 ± 2 ℃, placing half an hour, on electronic tensile machine, survey its 180 ° of stripping strengths, the peeling rate of electron detachment intensity machine is 0.5cm/s, and triplicate is averaged and is 180 ° of intensity of sample.(2) hold the mensuration of gluing intensity
With width is that 25 centimetres tested Pressuresensitive Tape carefully sticks on (one is brassboard, and one is attached plate) on the immediate two boards.Pasting length on the test board is 25 centimetres, and the stickup length on the attached plate is 50-60 centimetre.
After the coupons of above-mentioned preparation at room temperature put half an hour, it is hung vertically in constant temperature on the testing jig under the probe temperature again, hangs the weight of a heavy 1000g in the tag lower end, the record suspension time is holds sticking intensity.
Pressure sensitive adhesive of the present invention is rapid polymerization crosslinking under the radiation of UV-light, does not adopt water or common organic solvent, does not have any harmful volatile component, and need not special dry solidification and handle, be a kind of pressure-sensitive adhesive to the environment friendliness.
Embodiment:
Embodiment 1-9:
With 36.5 gram Isooctyl acrylate monomers; 53 gram butyl acrylates and 4 gram glytidyl methacrylate are mixed; get mixture 1/3 with a certain amount of dehydrated alcohol (consumption sees the following form) and 1.5 the gram benzoyl peroxides mix; add and be equipped with in the there-necked flask of reflux exchanger; add a certain amount of n-dodecyl mercaptan (consumption sees the following form); heat temperature raising to 82 ℃; refluxed 15 minutes; 2/3 monomer of measuring with remainder slowly splashed in the reaction flask with three hours again; keep the half an hour of refluxing after monomer drips off again, cooling discharging is performed polymer [1].
Gained performed polymer [1] is mixed with the triethylene Glycol diacrylate (TE) of 2 grams and the butyl acrylate (BA) of 10 grams, add the light trigger D-1173 of 3 grams and the trolamine of 3 grams, mixing makes the system viscosity maintain 2500 centipoises, be applied on the PET film evenly, place under the 750W ultraviolet lamp 15 centimeters to solidify 2 minutes.
The viscosity of the molecular weight control embodiment dodecyl sulphur anhydrous hexanol consumption system of tackiness agent is held viscous force
Alcohol consumption (%) is (cps) (min) 1 0.5 10＞100,000 31.22 0.7 10 12,200 20.33 0.75 10 7,300 15.24 0.8 10 3,500 5.15 0.9 10 2,850 0.56 0.5 15 42,000 21.57 0.5 20 15,200 17.88 0.5 25 6,700 10.29 0.5 30 3,700 2.0 (%)
As can be seen from the table, along with the increase of n-dodecyl mercaptan consumption, the viscosity of system reduces, and the viscous force of holding of pressure sensitive adhesive obviously reduces.Anhydrous hexanol also has similar effects.
Embodiment 10-14:
With 36.5 gram Isooctyl acrylate monomers; 53 gram butyl acrylates and 4 gram glytidyl methacrylate are mixed; get mixture 1/3 and 10 the gram dehydrated alcohols and 1.5 the gram benzoyl peroxides mix; add and to be equipped with in the there-necked flask of reflux exchanger, add 0.2 gram n-dodecyl mercaptan, heat temperature raising to 82 ℃; refluxed 15 minutes; 2/3 monomer of measuring with remainder slowly splashed in the reaction flask with three hours again, kept the half an hour of refluxing after monomer drips off again, and cooling discharging is performed polymer [1].
Performed polymer [1] is heated to 115 ℃, adds the tetraethylammonium bromide of 0.3 gram, the 2.6-ditertbutylparacresol of 0.3 gram. slowly be added dropwise to vinylformic acid 10 grams, keep 110 ℃ of reactions of temperature of reaction 2 hours, obtain the performed polymer [2] of acrylated.
The diluting monomer mixture of TE and BA, TE: BA=2: 5 (parts by weight), ratio with different performed polymer and thinner, add the light trigger D-1173 of 3 grams and the trolamine of 3 grams again, mixing makes the system viscosity maintain 4000 centipoises, be applied on the PET film evenly, place under the 750W ultraviolet lamp 15 centimeters to solidify 1.5 minutes.Obtain the pressure sensitive adhesive of uV curable.
The diluting monomer consumption is to tackiness agent Effect on Performance embodiment performed polymer: 180 ° of stripping strengths of thinner are held viscous force
(N/25cm) (hour)10 1∶0.2 1.25 ＞4811 1∶0.25 1.54 ＞4812 1∶0.30 0.78 ＞4813 1∶0.35 0.76 ＞4814 1∶0.40 1.08 ＞48
As can be seen from the table, the consumption that changes diluting monomer is also not obvious to the performance impact of pressure sensitive adhesive, and holding of tackiness agent glued intensity all greater than 48 hours, and the stripping strength of tackiness agent changes also less.
Claims (8)
1. the preparation method of a UV-light solidified pressure-sensitive adhesive, in weight part, carry out successively according to the following steps:
(1) preparation of performed polymer
With soft monomer 40-90% (weight percent)
Hard monomer 5-45% (weight percent)
Function monomer 2-15% (weight percent)
Be mixed into 100 parts acrylate monomer blend, get wherein 30-50 part with after the benzoyl peroxide of 5-40 part solvent and 1-5 part mixes, join in the reactor, the free radical chain transfer agent stirring heating backflow of adding 0.1-1.5 part 5-20 minute, drip remaining acrylate monomer blend, after dripping off in 1-4 hour, back flow reaction 0.5-1.5 hour again, be performed polymer after the cooling;
(2) preparation of pressure sensitive adhesive
Acrylate with 5-100 part is done monomer diluent, adds light trigger and light-initiated auxiliary agent and mixes, and the light trigger consumption is generally 1-5 part, and light-initiated auxiliary dosage is generally 1-5 part; Add 100 parts of performed polymers again, the system viscosity of making maintains the 1000-5000 centipoise, evenly is applied on the matrix, places to press radiation curing under the ultra-violet lamp;
Described soft monomer is the alkyl alcohol acrylate that contains 4-20 carbon atom;
Described hard monomer is: methyl acrylate (MA), methyl methacrylate (MMA), vinyl-acetic ester (VAc), vinylbenzene (St), acrylonitrile (AN), Jia Jibingxisuanyizhi (EMA) or n-BMA (BMA);
Described function monomer is: vinylformic acid, toxilic acid or maleic anhydride, (methyl) acrylamide, (methyl) propenoic acid beta-hydroxy ethyl ester or (methyl) propenoic acid beta-hydroxy propyl ester, (methyl) acrylic acid epoxy propyl ester, N hydroxymethyl acrylamide, methylene-succinic acid, multicondensed ethylene glycol double methyl methacrylate, Vinylstyrene.
2. according to the preparation method of claim 1, it is characterized in that: described soft monomer is n-butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate.
3. according to the preparation method of claim 1, it is characterized in that: described free radical chain transfer agent is a n-dodecyl mercaptan, uncle's lauryl mercaptan.
4. according to the preparation method of claim 1, it is characterized in that: described solvent is tetracol phenixin, dimethylbenzene, ethanol, anhydrous methanol, Virahol or its mixture.
5. according to the preparation method of claim 1, it is characterized in that: the light trigger consumption is 1-5 part, and light-initiated auxiliary dosage is 1-5 part.
6. according to the preparation method of claim 1, it is characterized in that: described light trigger is benzoin methyl ether, Benzoin ethyl ether, st-yrax n-butyl ether, benzophenone, D-1173 (Ciba).
7. according to the preparation method of claim 1, it is characterized in that: described light-initiated auxiliary agent is triethylamine, diethylamine, diethanolamine, trolamine.
8. according to the preparation method of claim 1, it is characterized in that: further in performed polymer more than 100 parts, add 0.1-1 part four hexyl amine bromides and make catalyzer, be heated to 110-115 ℃ of vinylformic acid that slowly splashes into 1-15 part, drip off the back and continue reaction 0.5-2 hour, obtain acrylated performed polymer.
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| CN 01120215 CN1394928A (en) | 2001-07-06 | 2001-07-06 | Preparation method of UV-light solidified pressure-sensitive adhesive |
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| CN 01120215 CN1394928A (en) | 2001-07-06 | 2001-07-06 | Preparation method of UV-light solidified pressure-sensitive adhesive |
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