CN107936903A - A kind of ultraviolet photo-curing cementing agent and its preparation method and application - Google Patents
A kind of ultraviolet photo-curing cementing agent and its preparation method and application Download PDFInfo
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- CN107936903A CN107936903A CN201710879853.0A CN201710879853A CN107936903A CN 107936903 A CN107936903 A CN 107936903A CN 201710879853 A CN201710879853 A CN 201710879853A CN 107936903 A CN107936903 A CN 107936903A
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- acrylate
- cured adhesive
- ultraviolet cured
- methacrylate
- polyether
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
Abstract
The invention belongs to electronic material Structural Adhesive Technique ' field, discloses a kind of preparation method and application of ultraviolet photo-curing cementing agent.The ultraviolet cured adhesive includes following components：Polyether-based ultra-branched polyurethane acrylate 50~90%, esters of acrylic acid reactive diluent 5~35%, photoinitiator 1~8%, thixotroping powder 1~15% and auxiliary agent 1~10%.The ultraviolet cured adhesive of the present invention uses ultraviolet light-initiated chain polymerization, and hardening time is short, and general hardening time is 5~15 seconds, and production efficiency is high；It is suitable for lens in LED light bar to be adhesively fixed, the balance of toughness, bonding force, temperature tolerance and moisture-proof can be taken into account at the same time.
Description
Technical field
The invention belongs to electronic material Structural Adhesive Technique ' field, more particularly to a kind of preparation of ultraviolet photo-curing cementing agent
Methods and applications.
Background technology
LED television becomes the mainstream television set of existing market due to having the advantages that energy saving, small, cost is low etc.,
The key core product of LED television is light Bar, i.e. LED light bar, it is welded on LED light on elongated aluminum substrate, so
Afterwards by PC lens caps in LED light, be uniformly distributed the light of LED, PC lens by three pins be fixed on glass substrate or
On aluminum substrate.
The PC lens bonding of LED television is general at present uses single-component epoxy glue sticking, and major defect is to need -20 DEG C of left sides
Right low tempertaure storage, storage and transport are inconvenient, and hardening time needs 3-5 minutes, low production efficiency, and need at 110 DEG C
The curing of left and right, energy consumption are serious.
Single-component epoxy glue sticking lens are replaced using UV glue, can transport and store in room temperature, hardening time is short (5-15 seconds),
Room temperature UV cures, and saves the energy.
A kind of curable adhesive of invention how gushed et al. in Shandong Marine Paints research institute, by elastomer epoxy acrylic tree
Fat, mono-functional reactive's diluent, polyfunctional group reactive diluent, photosensitizer and auxiliary agent composition, are mainly used for the bonding of glass,
It is typically applied in LCD sealing liquid crystals and uses (publication number：CN1199075A).
A kind of ultraviolet cured adhesive prepared by Pan Guangjun of Yantai moral nation et al. inventions, by the raw material of following percentage by weight
Composition：The polybutadiene-modified acrylate 25~50% of high-vinyl-content, the liquid polybutadiene tree of high-vinyl-content
Fat 20-50%, esters of acrylic acid reactive diluent 20~50%, photoinitiator 2~7%.The ultraviolet cured adhesive solves often
Ultraviolet cured adhesive is advised in the incomplete shortcoming of black plastic interface solidification, curing degree is high, and condensate performance is excellent, and bonding can
The high, (publication number applied widely by property：CN103952086A).But it is applied in light Bar lens bonding, toughness
Deficiency, heatproof are poor.
A kind of curable adhesive is invented in care of Guangdong Hengda New Materials Technology Co., Ltd et al., by following weight hundred
Divide the raw material composition of ratio：Polyether based polyurethanes acrylate or polybutadiene-modified acrylate 10~75%, polyurethane propylene
Acid esters or epoxy acrylate 5-50%, esters of acrylic acid reactive diluent 10~70%, photoinitiator 1~10%.This is ultraviolet
Optic-solidified adhesive mainly solves the bonding of glass and aluminium cake in glass furniture, solves the problems, such as that adhesive high-temp resisting high-humidity resisting performance is bad
(publication number：CN101392152A).But it is applied in light Bar lens bonding, to the plastic material bonding force such as lens
Not enough.
Cui Hengli of Yantai moral nation et al. invents a kind of liquid crystal display television side frame ultraviolet cured adhesive, viscosity for 15000~
50000mPa.s, thixotropic index 1.2~4, is bound up by the raw material of following parts by weight：Make bifunctionality polyurethane acroleic acid by oneself
20~40 parts of ester performed polymer, 5~30 parts of self-control inertia base polyurethane prepolymer for use as, 10~30 parts of nitrogenous functional monomer, single functionality
10~30 parts of acrylate monomer, 1~5 part of bifunctionality acrylate monomer, 1~5 part of photoinitiator, fumed silica
1~5 part, 1~4 part of silane coupling agent；Wherein described self-control bifunctionality polyurethane acrylate prepolymer includes polyester binary
Alcohol, diisocyanate, catalyst, polymerization inhibitor, antioxidant, hydroxy acryl acid ester, and polyester diol：Diisocyanate：Contain
Hydroxy acrylate is 1：1.2~2.0：0.4~2.0 (molar ratio), catalyst, polymerization inhibitor and antioxidant respectively account for the double officials of self-control
0.1 ‰~the 1 ‰ of energy degree polyurethane acrylate prepolymer weight；The self-control inertia base polyurethane prepolymer for use as includes polyester binary
Alcohol, diisocyanate, catalyst, polymerization inhibitor, antioxidant, monohydric alcohol, and polyester diol：Diisocyanate：Monohydric alcohol is 1：
1.5~2.0：1.0~2.0 (molar ratios), catalyst, polymerization inhibitor and antioxidant respectively account for self-control inertia polyurethane prepolymer body weight
0.1 ‰~1 ‰ (publication numbers：CN103525355A).The glue toughness and temperature tolerance are excellent, but bonding force is insufficient.
Li Yinglin of Guangzhou Huitian Fine Chemical Co., Ltd. et al. is poly- with isophorone diisocyanate IPDI, modification
Ethoxylated polyhydric alcohol, hydroxyethyl methacrylate (HEMA) are primary raw material, urethane acrylate are prepared for, for a kind of high-performance
Ultraviolet photo-curing cementing agent, adhesive strength is excellent, but weather resistance it is poor (" a kind of high-performance ultraviolet cured adhesive
Prepare ", bonding, 09 phase in 2014).UV glue is major problem is that toughness, bonding force, temperature tolerance and moisture-proof cannot be taken into account at present
Property.
The content of the invention
In order to overcome shortcoming and defect existing in the prior art, primary and foremost purpose of the invention is to provide a kind of ultraviolet light
Cured adhesive.The ultraviolet photo-curing cementing agent replaces single-component epoxy glue sticking lens, and the ultraviolet cured adhesive is through ultraviolet light
, can be by PC or PMMA lens strong bonds in LED light bar after curing, while take into account toughness, bonding force, temperature tolerance and moisture-proof
Balance.
It is still another object of the present invention to provide a kind of preparation method of above-mentioned ultraviolet photo-curing cementing agent.
A further object of the present invention is to provide a kind of application of above-mentioned ultraviolet photo-curing cementing agent.
The purpose of the present invention is achieved through the following technical solutions：
A kind of ultraviolet cured adhesive, the ultraviolet cured adhesive include following components：Polyether-based surpasses
Branched polyurethanes acrylate 50~90%, esters of acrylic acid reactive diluent 5~35%, photoinitiator 1~8%, thixotroping powder 1
~15% and auxiliary agent 1~10%.
Preferably, which includes following components：Polyether-based super branched polyurethane
Acrylate 60~80%, esters of acrylic acid reactive diluent 10~30%, photoinitiator 2~6%, 1~10% and of thixotroping powder
Auxiliary agent 1~8%.
Preferably, which includes following components：Polyether-based super branched polyurethane
Acrylate 65~75%, esters of acrylic acid reactive diluent 15~25%, photoinitiator 3~5%, thixotroping powder 2~6% and help
Agent 1~5%.
The polyether-based ultra-branched polyurethane acrylate is specifically prepared by following methods：
The first step, adds reaction kettle, while stirring by polyether polyol, 2,2- dihydromethyl propionic acids, p-methyl benzenesulfonic acid
By kettle temperature rise to 135~145 DEG C of reactions 2~3 it is small when, the then lower reaction of vacuum distillation be below 9mg/g KOH to acid number, is cooled down
Superbrnaching end-hydroxy polyether type polyester is obtained after purification；
Second step, by Toluene-2,4-diisocyanate, 4- diisocyanate, hydroxy acrylate, acetone, polymerization inhibitor and di lauric dibutyl
Tin adds another reaction kettle, measures initial nco value, when normal-temperature reaction 2~4 is small after, being warming up to 45~55 DEG C, the reaction was continued, extremely
Nco value stops when being initial value half, is cooled to room temperature；
3rd step, second step reaction kettle is added by superbrnaching end-hydroxy polyether type polyester obtained by the first step, while adds two
Dibutyl tin laurate, be warming up to 50~55 DEG C reaction to NCO mass contents be less than 0.1% when, vacuum outgas, obtains polyether-based
Ultra-branched polyurethane acrylate.
For the molecular weight of polyether polyol described in the first step between 500~2000, average functionality is 2~3, and ether chain is
At least one of ethylene oxide (EO), propylene oxide (PO) and epoxy butane (BO).
Hydroxy acrylate described in second step is hydroxy ethyl methacrylate, hydroxyethyl meth acrylate, hydroxypropyl
At least one of acrylate and hydroxypropyl methacrylate；The polymerization inhibitor for hydroquinone, p-hydroxyanisole,
At least one of 2,5- dimethyl hydroquinones and 1,4- naphthalenediols.
Preferably, the polyether-based ultra-branched polyurethane acrylate being prepared should seal be kept in dark place it is spare.
The esters of acrylic acid reactive diluent is lauryl acrylate, lauryl methacrylate, 2- phenoxy group second
Base acrylate, 2- phenoxyethyl methacrylates, ethoxyquin phenoxy group acrylate, ethoxyquin phenoxymethyl propylene
Acid esters, trimethyl cyclohexyl acrylate, trimethyl cyclohexylmethyl acrylate, ethoxyethoxyethyl acrylate,
Ethoxyethoxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, three hydroxyl of ring
Methylpropane dimethoxym ethane acrylate, ring trimethylolpropane dimethoxym ethane methacrylate, stearyl acrylate acid esters, methyl-prop
In olefin(e) acid stearate, decyl acrylate, decyl-octyl methacrylate, isobornyl acrylate and isobornyl methacrylate
It is at least one；Preferably, the esters of acrylic acid reactive diluent is lauryl acrylate, lauryl methacrylate, 2-
Phenoxyethyl acrylate, 2- phenoxyethyl methacrylates, ethoxyethoxyethyl acrylate, ethyoxyl second
Epoxide ethylmethyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate
At least one of with isobornyl methacrylate；
The photoinitiator is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 2,2-
Dimethoxy -2- phenyl acetophenones, 2,4,6- trimethylbenzoy-diphenies phosphine oxide, four (2,4- di-tert-butyl-phenyls) -
4,4 '-xenyl bis-phosphite, 2- methyl isophthalic acids-(4- methyl mercaptos phenyl) -2- morpholinyl -1- acetone, 2- phenyl benzyl -2- diformazans
In base amino -1- (4- morpholine benzyls phenyl) butanone, isopropyl thioxanthone, benzophenone and ethyl 4-dimethylaminobenzoate
At least one；
The thixotroping powder is nano-calcium carbonate, aerosil, bentonite, cellulose acetate, polymer elasticity grain
At least one of son and polyamide, are preferably at least one of aerosil, polyamide and polymer elasticity particle；
The auxiliary agent is at least one of adhesion promoter, wetting dispersing agent and defoamer.The attachment is made every effort to promote
It is silane coupling agent or phosphoester acrylic ester into agent；The wetting dispersing agent is esters of acrylic acid wetting dispersing agent；It is described to disappear
Infusion is esters of acrylic acid defoamer.
The preparation method of above-mentioned ultraviolet cured adhesive, includes step in detail below：Successively by percentage by weight 65~75%
Polyether-based ultra-branched polyurethane acrylate, the esters of acrylic acid reactive diluent of percentage by weight 15~25%, weight hundred
Photoinitiator, the thixotroping powder of percentage by weight 2~6% and the auxiliary agent of percentage by weight 1~5% than 3~5% is divided to be put in mixing
In machine, stirring is vacuumized after stirring evenly to bubble-free, stands to room temperature, obtains ultraviolet cured adhesive.
Preferably, the ultraviolet cured adhesive being prepared loads black or the packing material interior sealing of dark impermeable ultraviolet light is protected
Deposit, room temperature storage.
Application of the above-mentioned ultraviolet cured adhesive in LED television light Bar lamp bar lens are adhesively fixed.
The ultraviolet cured adhesive of the present invention can be used in addition to being bonded for LED television light Bar lamp bars lens
Other known similar applications.
The ultraviolet cured adhesive is bonded lens, after being cured by ultraviolet light, more than lens thrust 180N, 1.5 meters
Freely falling body does not fall part three times, 85 DEG C, 85%RH storages 1000 it is small when more than thrust 120N, -40 DEG C of ﹒ 30min~100 DEG C ﹒
100 circulation more than thrust 120N of 30min thermal shocks.
The present invention is had the following advantages relative to the prior art and beneficial effect：
(1) ultraviolet cured adhesive of the invention uses ultraviolet light-initiated chain polymerization, saves the energy；
(2) ultraviolet cured adhesive of the invention does not discharge organic gas completely, more environmentally-friendly；
(3) ultraviolet cured adhesive hardening time of the invention is short, and general hardening time is 5~15 seconds, and production efficiency is high；
(4) refrigerated storage is not required in the ultraviolet cured adhesive that the present invention is prepared, and transport and storage are more convenient；
(5) ultraviolet cured adhesive that the present invention is prepared can firmly glue PC or PMMA lens relative to traditional UV glue
It is connected in LED light bar, while takes into account the balance of toughness, bonding force, temperature tolerance and moisture-proof.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Synthesis example 1：
In glass four-hole boiling flask of 500 milliliters equipped with blender, thermometer and condenser pipe, VORANOL 2070 is added
93 grams of (Dow Chemical, average molecular weight 700, degree of functionality 3, intermediate molecular weight triol), 2,2- dihydromethyl propionic acids 375
Gram, 0.47 gram of p-methyl benzenesulfonic acid, under stirring by kettle temperature rise to 142 DEG C of reactions 2 it is small when, the then lower reaction of vacuum distillation to acid number
For below 9mg/g KOH, cooling obtains superbrnaching end-hydroxy polyether type polyester A1 after purification.
In the glass four-hole boiling flask of clean dried of 500 milliliters equipped with blender, thermometer and condenser pipe, add
140 grams of Toluene-2,4-diisocyanates, 4- diisocyanate, 104 grams of hydroxypropyl acrylates, 0.25 gram of hydroquinone and 0.3 gram of two fourth of tin dilaurate
Ji Xi, 125 milliliters of acetone, measures initial nco value, when normal-temperature reaction 3 is small after, being warming up to 48 DEG C, the reaction was continued, is to nco value
Stop during initial value half, be cooled to room temperature；Add 96 grams of superbrnaching end-hydroxy polyether type polyester A1 and 0.15 gram of tin dilaurate
Dibutyl tin, be warming up to 52 DEG C reaction to NCO mass contents be less than 0.1% when, vacuum outgas, obtains polyether-based hyperbranched poly ammonia
Ester acrylate B1.
Synthesis example 2：
In glass four-hole boiling flask of 500 milliliters equipped with blender, thermometer and condenser pipe, VORANOL 2120 is added
200 grams of (Dow Chemical, average molecular weight 2000, degree of functionality 2, polypropylene glycol), 2,2- dihydromethyl propionic acids 187.5
Gram, 0.39 gram of p-methyl benzenesulfonic acid, under stirring by kettle temperature rise to 145 DEG C of reactions 2.5 it is small when, the then lower reaction of vacuum distillation to acid
It is worth and obtains superbrnaching end-hydroxy polyether type polyester A2 after purification for below 9mg/g KOH, cooling.
In the glass four-hole boiling flask of clean dried of 500 milliliters equipped with blender, thermometer and condenser pipe, add
140 grams of Toluene-2,4-diisocyanates, 4- diisocyanate, 92.8 grams of hydroxy-ethyl acrylates, 0.3 gram of p-hydroxyanisole and 0.3 gram of tin dilaurate
Dibutyl tin, 150 milliliters of acetone, measures initial nco value, when normal-temperature reaction 2 is small after, being warming up to 55 DEG C, the reaction was continued, to NCO
It is worth to stop during initial value half, is cooled to room temperature；Add 148 grams of superbrnaching end-hydroxy polyether type polyester A2 and 0.1 gram of February
Dilaurylate, be warming up to 55 DEG C reaction to NCO mass contents be less than 0.1% when, vacuum outgas, it is hyperbranched to obtain polyether-based
Urethane acrylate B2.
Synthesis example 3：
In glass four-hole boiling flask of 500 milliliters equipped with blender, thermometer and condenser pipe, VORANOL 222- are added
056 200 grams of (Dow Chemical, average molecular weight 2000, degree of functionality 2, polyethylene glycol), 2,2- dihydromethyl propionic acids
187.5 grams, 0.39 gram of p-methyl benzenesulfonic acid, under stirring by kettle temperature rise to 135 DEG C of reactions 3 it is small when, the then lower reaction of vacuum distillation
It is below 9mg/g KOH to acid number, cooling obtains superbrnaching end-hydroxy polyether type polyester A3 after purification.
In the glass four-hole boiling flask of clean dried of 500 milliliters equipped with blender, thermometer and condenser pipe, add
140 grams of Toluene-2,4-diisocyanates, 4- diisocyanate, 104 grams of hydroxypropyl acrylates, 0.25 gram of hydroquinone and 0.25 gram of two fourth of tin dilaurate
Ji Xi, 150 milliliters of acetone, measures initial nco value, when normal-temperature reaction 4 is small after, being warming up to 45 DEG C, the reaction was continued, is to nco value
Stop during initial value half, be cooled to room temperature；Add 145 grams of superbrnaching end-hydroxy polyether type polyester A3 and 0.2 gram of tin dilaurate
Dibutyl tin, be warming up to 50 DEG C reaction to NCO mass contents be less than 0.1% when, vacuum outgas, obtains polyether-based hyperbranched poly ammonia
Ester acrylate B3.
Embodiment 1-6 and comparative example 1-2：
Polyether-based ultra-branched polyurethane acrylate (the B1- that synthesis example 1-3 is prepared is sequentially added in 2L planet machines
B3), esters of acrylic acid reactive diluent, photoinitiator, thixotroping powder and auxiliary agent, after high speed dispersion stirs evenly, vacuumize stirring
To bubble-free, stand to room temperature, obtain ultraviolet cured adhesive, load the packing material interior sealing of black or dark impermeable ultraviolet light
Preserve, room temperature storage.
Component proportion by weight percentage, is specifically shown in Table 1 in embodiment 1-6 and comparative example 1-2.Resin is selected certainly
Polyether-based ultra-branched polyurethane acrylate (B1-B3) processed and Taiwan Changxing urethane acrylate 6195-100, acrylate
Class reactive diluent selects EM210 (2- phenoxyethyl acrylates), EM214 (the tetrahydrofurfuryl acrylic acid in Taiwan Changxing
Ester), EM212 (ring trimethylolpropane dimethoxym ethane acrylate), photoinitiator selects the Irgacure184 of Germany BASF, tactile
Become powder and select U.S. CARBOT aerosil TS720, adhesion promoter selects U.S. SARTOMER phosphate acrylic acid
Ester CD9051.
1 ultraviolet cured adhesive of table matches
The adhesive strength of ultraviolet cured adhesive in testing example 1~6, comparative example 1~2, toughness and resistance to by the following method
Warm moisture resistance properties.Method for making sample：The ultraviolet cured adhesive of preparation is fixed by syringe point in the corresponding lens pin of LED light bar
On position, each fixed bit glue amount is controlled in 8 ± 0.5mg, is covered lens, is then 365nm ultraviolet lights by dominant wavelength, purple
Light intensity 80mW/cm during outer photocuring2, light application time 15s.23 ± 1 DEG C, tested under the conditions of 50 ± 5%RH 1. parallel with LED light bar
The lens thrust in direction；2. by the placement parallel to the ground of the LED light bar of bonding lens, liftoff 1.5 meters of freely falling bodies three times, are seen
Examine whether lens loosen, there are one or more lens to loosen, be denoted as NG, whole lens do not loosen, are denoted as OK；3. by LED light
Bar is placed in climatic chamber, 85 DEG C, 85%RH storages 1000 it is small when after, 23 ± 1 DEG C, place one under the conditions of 50 ± 5%RH
Lens thrust is surveyed after it；4. LED light bar is placed in thermal shock case, from room temperature be down to -40 DEG C keep 30 minutes after, heating
After being kept for 30 minutes to 100 DEG C, be cooled to room temperature be a circulation (cooling rate is 2 DEG C/min, programming rate is 10 DEG C/
Min), after 100 circulations, 23 ± 1 DEG C, places one day under the conditions of 50 ± 5%RH after survey lens thrust.Test result such as table
(wherein thrust represents bonding force, drop test feedback toughness, hot and humid experiment feedback resistance to gentle moisture-proof, cold and hot punching shown in 2
Hit experiment feedback temperature tolerance and toughness)：
The performance test results of 2 ultraviolet cured adhesive of table
By table 2 as it can be seen that the ultraviolet cured adhesive of the present invention has excellent bonding force, PC or PMMA lens can firmly be glued
It is connected in LED light bar, while takes into account the balance of toughness, bonding force, temperature tolerance and moisture-proof.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. ultraviolet cured adhesive, it is characterised in that：The ultraviolet cured adhesive includes following components： Polyether-based ultra-branched polyurethane acrylate 50~90%, esters of acrylic acid reactive diluent 5~35%, photoinitiator 1~ 8%th, thixotroping powder 1~15% and auxiliary agent 1~10%.
- A kind of 2. ultraviolet cured adhesive according to claim 1, it is characterised in that：The ultraviolet cured adhesive is included and pressed below The component of percentage by weight meter：Polyether-based ultra-branched polyurethane acrylate 60~80%, esters of acrylic acid reactive diluent 10 ~30%, photoinitiator 2~6%, thixotroping powder 1~10% and auxiliary agent 1~8%.
- A kind of 3. ultraviolet cured adhesive according to claim 1, it is characterised in that：The ultraviolet cured adhesive is included and pressed below The component of percentage by weight meter：Polyether-based ultra-branched polyurethane acrylate 65~75%, esters of acrylic acid reactive diluent 15 ~25%, photoinitiator 3~5%, thixotroping powder 2~6% and auxiliary agent 1~5%.
- A kind of 4. ultraviolet cured adhesive according to claim 1, it is characterised in that：The polyether-based super branched polyurethane Acrylate is specifically prepared by following methods：The first step, adds reaction kettle, while stirring by kettle by polyether polyol, 2,2- dihydromethyl propionic acids, p-methyl benzenesulfonic acid Temperature rise to 135~145 DEG C of reactions 2~3 it is small when, the then lower reaction of vacuum distillation be below 9mg/g KOH to acid number, and cooling purifies After obtain superbrnaching end-hydroxy polyether type polyester；Second step, by Toluene-2,4-diisocyanate, 4- diisocyanate, hydroxy acrylate, acetone, polymerization inhibitor and dibutyl tin laurate add Enter another reaction kettle, measure initial nco value, when normal-temperature reaction 2~4 is small after, being warming up to 45~55 DEG C, the reaction was continued, to nco value To stop during initial value half, room temperature is cooled to；3rd step, second step reaction kettle is added by superbrnaching end-hydroxy polyether type polyester obtained by the first step, while adds two bays Sour dibutyl tin, be warming up to 50~55 DEG C reaction to NCO mass contents be less than 0.1% when, vacuum outgas, obtain polyether-based over-expense Change urethane acrylate.
- A kind of 5. ultraviolet cured adhesive according to claim 4, it is characterised in that：Polyether polyol described in the first step For molecular weight between 500~2000, average functionality is 2~3, and ether chain is in ethylene oxide, propylene oxide and epoxy butane It is at least one.
- A kind of 6. ultraviolet cured adhesive according to claim 4, it is characterised in that：Hydroxy acrylic acid described in second step Ester is in hydroxy ethyl methacrylate, hydroxyethyl meth acrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate It is at least one；The polymerization inhibitor is in hydroquinone, p-hydroxyanisole, 2,5- dimethyl hydroquinones and 1,4- naphthalenediols At least one.
- A kind of 7. ultraviolet cured adhesive according to claim 1, it is characterised in that：The esters of acrylic acid activity dilution Agent is lauryl acrylate, lauryl methacrylate, 2- phenoxyethyl acrylates, 2- Phenoxyethyl methacrylic acids Ester, ethoxyquin phenoxy group acrylate, ethoxyquin phenoxymethyl acrylate, trimethyl cyclohexyl acrylate, trimethyl Cyclohexylmethyl acrylate, ethoxyethoxyethyl acrylate, ethoxyethoxyethyl methacrylate, tetrahydrochysene Change furfuryl acrylic acid ester, tetrahydrofurfuryl methacrylate, ring trimethylolpropane dimethoxym ethane acrylate, ring trihydroxy methyl Propane dimethoxym ethane methacrylate, stearyl acrylate acid esters, stearyl methacrylate, decyl acrylate, metering system At least one of sour last of the ten Heavenly stems ester, isobornyl acrylate and isobornyl methacrylate；The photoinitiator is 1- hydroxyls Cyclohexyl phenyl ketone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 2,2- dimethoxy -2- phenyl acetophenones, 2,4,6- tri- Methyl benzoyl-diphenyl phosphine oxide, four (2,4- di-tert-butyl-phenyls) -4,4 '-xenyl bis-phosphites, 2- methyl - 1- (4- methyl mercaptos phenyl) -2- morpholinyl -1- acetone, 2- phenyl benzyl -2- dimethylaminos -1- (4- morpholine benzyls phenyl) butanone, At least one of isopropyl thioxanthone, benzophenone and ethyl 4-dimethylaminobenzoate；The thixotroping powder is to receive At least one of rice calcium carbonate, aerosil, bentonite, cellulose acetate, polymer elasticity particle and polyamide；Institute The auxiliary agent stated is at least one of adhesion promoter, wetting dispersing agent and defoamer.
- A kind of 8. ultraviolet cured adhesive according to claim 7, it is characterised in that：The esters of acrylic acid activity dilution Agent is lauryl acrylate, lauryl methacrylate, 2- phenoxyethyl acrylates, 2- Phenoxyethyl methacrylic acids Ester, ethoxyethoxyethyl acrylate, ethoxyethoxyethyl methacrylate, tetrahydrofurfuryl acrylate, At least one of tetrahydrofurfuryl methacrylate, isobornyl acrylate and isobornyl methacrylate；Described Thixotroping powder is at least one of aerosil, polyamide and polymer elasticity particle；The adhesion promoter is silicon Alkane coupling agent or phosphoester acrylic ester；The wetting dispersing agent is esters of acrylic acid wetting dispersing agent；The defoamer is third Olefin(e) acid esters defoamer.
- A kind of 9. preparation method according to claim 1~8 any one of them ultraviolet cured adhesive, it is characterised in that comprising with Lower specific steps：Successively by the polyether-based ultra-branched polyurethane acrylate of percentage by weight 65~75%, percentage by weight 15 ~25% esters of acrylic acid reactive diluent, the photoinitiator of percentage by weight 3~5%, percentage by weight 2~6% touch The auxiliary agent for becoming powder and percentage by weight 1~5% is put in mixer, and stirring is vacuumized after stirring evenly to bubble-free, is stood extremely After room temperature, ultraviolet cured adhesive is obtained.
- 10. it is bonded according to claim 1~8 any one of them ultraviolet cured adhesive in LED television light Bar lamp bars lens Application in fixation.
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| CN110791251A (en) * | 2019-10-30 | 2020-02-14 | 广东普赛达密封粘胶有限公司 | Acrylate modified polyurethane sealant and preparation method thereof |
| CN111534267A (en) * | 2020-04-15 | 2020-08-14 | 广州回天新材料有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
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| CN112341980A (en) * | 2020-10-05 | 2021-02-09 | 厦门韦尔通科技有限公司 | Acid-resistant alkali-resistant ultraviolet-curing peelable glue suitable for secondary anode process after deplating and preparation method thereof |
| CN112745798A (en) * | 2020-12-09 | 2021-05-04 | 浙江华正能源材料有限公司 | Photo-curing adhesive for lithium battery aluminum plastic film and preparation method thereof |
| CN114907538A (en) * | 2022-06-27 | 2022-08-16 | 韦尔通(厦门)科技股份有限公司 | Ultraviolet curing resin, ultraviolet curing adhesive and preparation method thereof |
| CN115717043A (en) * | 2022-11-02 | 2023-02-28 | 佛山阳光逸采涂料科技有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
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| CN112063341A (en) * | 2020-09-14 | 2020-12-11 | 诺邦泰新材料(深圳)有限公司 | UV (ultraviolet) adhesive for high water resistance of electronic product and preparation method thereof |
| CN112341980A (en) * | 2020-10-05 | 2021-02-09 | 厦门韦尔通科技有限公司 | Acid-resistant alkali-resistant ultraviolet-curing peelable glue suitable for secondary anode process after deplating and preparation method thereof |
| CN112745798A (en) * | 2020-12-09 | 2021-05-04 | 浙江华正能源材料有限公司 | Photo-curing adhesive for lithium battery aluminum plastic film and preparation method thereof |
| CN114907538A (en) * | 2022-06-27 | 2022-08-16 | 韦尔通(厦门)科技股份有限公司 | Ultraviolet curing resin, ultraviolet curing adhesive and preparation method thereof |
| CN114907538B (en) * | 2022-06-27 | 2023-07-14 | 韦尔通科技股份有限公司 | Ultraviolet light curing resin, ultraviolet light curing adhesive and preparation method thereof |
| CN115717043A (en) * | 2022-11-02 | 2023-02-28 | 佛山阳光逸采涂料科技有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
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