CN103555261B - Ultraviolet curing adhesive and preparation method thereof - Google Patents
Ultraviolet curing adhesive and preparation method thereof Download PDFInfo
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- CN103555261B CN103555261B CN201310532274.0A CN201310532274A CN103555261B CN 103555261 B CN103555261 B CN 103555261B CN 201310532274 A CN201310532274 A CN 201310532274A CN 103555261 B CN103555261 B CN 103555261B
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Abstract
The invention discloses an ultraviolet curing adhesive which is characterized by comprising the following raw materials in parts by weight: 40-60 parts of acrylate-modified polyurethane resin, 2-10 parts of methacrylate modified liquid nitrile rubber, 20-40 parts of special cycloolefin acrylate monomer, 2-10 parts of acrylate or methacrylate monomer containing functional groups, 1-5 parts of photoinitiator, 1-5 parts of vapor phase method silica, 0.5-2 parts of silane coupling agent, 0.01-0.1 part of pyrogallic acid and 0.001-0.01 part of stabilizer. Compared with the prior art, the ultraviolet curing adhesive provided by the invention has high bonding strength and high yellowing resistance and is suitable for adhesion of light-emitting diode (LED) backlight lens.
Description
Technical field
The present invention relates to adhesive techniques field, relate in particular to structural adhesive of a kind of UV curable and preparation method thereof.
Background technology
In recent years, LED(photodiode) backlight technology development is perfect, progressively enters industrialization.Compare CCFL(cathode fluorescent tube), LED has obvious power savings advantages, and colour gamut is wider, and the life-span is longer, and environmental protection more meets the frivolous propensity to consume easily of current electronic product more.In the products such as notebook, indicating meter and televisor, LED-backlit source will progressively replace CCFL backlight, become the main flow in market.Optical lens in LED-backlit module need to be combined with PCB substrate by binding agent.
Ultraviolet hardening binding agent has the advantage that curing speed is fast, cost is relatively low, is widely used in the reparation of glassware, the assembling of glass components and parts.Continuous expansion along with UV-curing technology Application Areas, all will play an important role at product middle-ultraviolet lamp curing binding agents such as mobile phone, televisor, computer, navigating instrument and Vehicular display devices.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of suitable thixotropy viscosity that has, high-adhesive-strength, and resistance to xanthochromia, is applicable to the bonding ultraviolet hardening structural adhesive of LED-backlit source lens; Another object of the present invention is to provide the preparation method of this ultraviolet hardening structural adhesive; The present invention also provides the using method of this ultraviolet hardening structural adhesive.
For realizing first goal of the invention, technical scheme provided by the invention is as follows: a kind of ultraviolet hardening structural adhesive, viscosity (Brookfield RV rotational viscosimeter, 20rpm, 25 ℃) be 5000～50000mPa.s, preferred 6000mPa.s～35000mPa.s, thixotropy index is 1.2～6, preferably 1.5～5, the raw material that contains following weight part: 40～60 parts of polymerization of acrylic modified polyurethane resins, 2～10 parts of methacrylic ester modified liquid paracrils, 20～40 parts of Special Ring olefin acrylate monomers, containing 2～10 parts of the acrylate of functional groups or methacrylate monomer, 1～5 part of light trigger, 1～5 part of fumed silica, 0.5～2 part of silane coupling agent, 0.01～0.1 part of pyrogallol, 0.001～0.01 part of stablizer.
The present invention is further, Hypro 1300X33LC or the Hypro 1300X43LC of described methacrylic ester modified liquid paracril WeiCVC company.
The present invention is further, the structure following (I) of described Special Ring olefin acrylate monomer:
The present invention is further, described pyrogallol structure following (II):
Adding of pyrogallol can not increase the thermotolerance that improves system under the prerequisite of solidifying energy.
The present invention is further, and the described acrylate containing functional groups or methacrylate monomer are a kind of or any several mixture in hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, glycidyl methacrylate, vinylformic acid-4-hydroxyl butyl ester, 2-hydroxyl-3-benzene oxygen propyl group acrylate, vinylformic acid caprolactone.
The present invention is further, and described stablizer is a kind of in ethylenediamine tetraacetic acid (EDTA) (EDTA), disodium ethylene diamine tetraacetate (EDTA-2Na), trisodium EDTA (EDTA-3Na), tetrasodium ethylenediamine tetraacetate (EDTA-4Na); During use, be mixed with the aqueous solution of 10% concentration.
The present invention is further, the TS-720 that described fumed silica is Cabot Co.,Ltd, TS-530, the R202 of Ying Chuan company, R972, R7200, R8200, a kind of or any several mixture in the H18 of Wa Ke company, H20.
The present invention is further, and described silane coupling agent is γ-methacryloxypropyl trimethoxy silane.
The present invention is further, and described light trigger is the mixture of 1-hydroxyl-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester.
For realizing second goal of the invention, the preparation method of this ultraviolet hardening structural adhesive of the present invention comprises the steps:
(1) polyester diol is vacuumized at the temperature of 110 ℃～120 ℃ to dehydration 1 hour～2 hours; Then add successively vulcabond, catalyzer, and fully stir at the temperature of 50 ℃～70 ℃, react 2 hours～3 hours; Then add successively again stopper, oxidation inhibitor, hydroxy acryl acid ester, and fully stir at the temperature of 60 ℃～80 ℃, continue reaction 2 hours～3 hours, until the absorption peak of isocyanate groups disappears in the infrared spectra that taking-up sample is recorded, then add reactive thinner, stir, cooling discharge, obtains polymerization of acrylic modified polyurethane resin;
(2) polymerization of acrylic modified polyurethane resin, methacrylic ester modified liquid paracril, Special Ring olefin acrylate monomer, the acrylate that contains functional groups or methacrylate monomer, stablizer, fumed silica are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2 hours～3 hours, system is mixed; Then add light trigger, silane coupling agent and pyrogallol, continue to stir 1 hour～2 hours vacuumizing and defoaming, discharging.
On the basis of technique scheme, the present invention is further, polyester diol in step (1): vulcabond: the mol ratio of hydroxy acryl acid ester is 1:1.2～2.0:0.4～2.0;
Described catalyzer, stopper, oxidation inhibitor all account for 0.1 ‰～1 ‰ of step (1) raw material total mass, and described reactive thinner accounts for 20%～50% of step (1) raw material total mass.
The present invention is further, and what described polyester diol was molecular weight in 500～3000 polydiethylene glycol adipate dibasic alcohol, poly adipate succinic acid ester dibasic alcohol, poly-hexanodioic acid compound polyhydric alcohol ester dibasic alcohol series, polycaprolactone dibasic alcohol, PCDL, fatty acid modified polyester diol is a kind of.
The present invention is further, and described vulcabond is tolylene diisocyanate, 4, a kind of in 4'-diphenylmethanediisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.
The present invention is further, described hydroxy acryl acid ester is senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, senecioate-hydroxy butyl ester, tertiary capric acid glycidyl ester acrylate, diethylene glycol monoacrylate, dipropylene glycol mono acrylic ester, 1, a kind of in ammediol mono acrylic ester, BDO mono acrylic ester.
The present invention is further, and described catalyzer is dibutyl tin laurate.
The present invention is further, and described stopper is MEHQ.
The present invention is further, and described oxidation inhibitor is β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester.
The present invention is further, described reactive thinner is a kind of or any several mixture in ethyl acrylate, 2-phenoxyethyl acrylate, vinylformic acid ethoxy ethoxy ethyl ester, lauryl acrylate, isobornyl acrylate, vinylformic acid tetrahydrofuran ester, N,N-DMAA, acryloyl morpholine.
For realizing the 3rd goal of the invention, it is bonding that this ultraviolet hardening binding agent provided by the invention can be applied to LED-backlit source lens, concrete steps are as follows: by ultraviolet hardening binding agent by some glue or silk screen printing on PCB substrate, again LED-backlit source lens is positioned on ultraviolet hardening binding agent, then by UV-irradiation, makes adhesive cures.
Further, the material of described lens is a kind of in glass, quartz, acrylic, polycarbonate.
Further, described uviolizing energy is at 3000mJ/cm
2below.
Compared with prior art, ultraviolet hardening binding agent provided by the invention has higher cohesive strength, and anti-yellowing property is good, is suitable for the bonding of LED-backlit source lens.
Embodiment
Testing method is as follows:
(1) mensuration of viscosity and thixotropy index
According to GB/T 2794-1995, the viscosity by Brookfield RV viscometer test glue sample under 2.5rpm and 20rpm, 25 ℃ of probe temperatures.The ratio of the viscosity under 2.5rpm under viscosity and 20rpm is thixotropy index;
(2) mensuration of yellowing resistance
Glue sample is coated on slide glass, and uviolizing is solidified, and puts into 90 ℃ of baking ovens 7 days, and the colour-change of observing aging front and back is evaluated according to following 3 grades:
Zero: without colour-change
△: colour-change is small, not obvious
*: colour-change is very obvious
(3) mensuration of thrust before and after reliability testing
Glue is put on PCB substrate, placed the lens of acrylic material, uviolizing is solidified, and tests its thrust.Make again in addition some exemplars, first in 85 ℃ * 85%RH ageing oven, place 500 hours, then continue thermal shock case (40 ℃ 100 ℃, place 168 circulations in 1h/cycle), take out and place at ambient temperature 30 minutes, then test its thrust.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
The polyester diol that is 215 by 100 grams of hydroxyl values (winning wound Oxyester EP-HS2272) joins in reactor, at the temperature of 110 ℃, vacuumize dehydration 1 hour, be cooled to below 40 ℃, add 48.8 grams of tolylene diisocyanates, 0.1 gram of dibutyl tin laurate, 50 ℃ of reactions 2 hours, add successively 0.3 gram of MEHQ, 0.45 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 19.5 grams of senecioate-hydroxyl ethyl esters, continuation was 60 ℃ of reactions 2 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 43g isobornyl acrylate, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU1].
40g polymerization of acrylic modified polyurethane resin [AU1], 2g methacrylic ester modified liquid paracril (the Hypro 1300X43LC of CVC company), 20g Special Ring olefin acrylate monomer, 2g hydroxyethyl methylacrylate, the EDTA-2Na aqueous solution of 0.01g10% concentration, 1.3g fumed silica (H18 of Wa Ke company) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2 hours, system is mixed; Then add 0.5g1-hydroxyl-cyclohexyl phenyl ketone, 0.5g2; 4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 0.5g γ-methacryloxypropyl trimethoxy silane and 0.01g pyrogallol, continue to stir 1 hour; vacuumizing and defoaming, discharging.
Embodiment 2
The polyester diol that is 107 by 100 grams of hydroxyl values (winning wound Oxyester T1136) joins in reactor, at the temperature of 115 ℃, vacuumize dehydration 1.5 hours, be cooled to below 40 ℃, add 33.3g isophorone diisocyanate, 0.1 gram of dibutyl tin laurate, 55 ℃ of reactions 2.5 hours, add successively 0.2 gram of MEHQ, 0.35 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 15.1 grams of senecioate-hydroxy butyl esters, continuation was 65 ℃ of reactions 2.5 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 55g vinylformic acid tetrahydrofuran ester, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU2].
44g polymerization of acrylic modified polyurethane resin [AU2], 4g methacrylic ester modified liquid paracril (the Hypro 1300X33LC of CVC company), 24g Special Ring olefin acrylate monomer, 4g glycidyl methacrylate, the EDTA-3Na aqueous solution of 0.03g10% concentration, 2.8g fumed silica (R202 of Ying Chuan company) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2.2 hours, system is mixed; Then add 4g1-hydroxyl-cyclohexyl phenyl ketone, 1g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 0.5g γ-methacryloxypropyl trimethoxy silane and 0.02g pyrogallol, continue to stir 1.2 hours vacuumizing and defoaming, discharging.
Embodiment 3
The polyester diol that is 56 by 100 grams of hydroxyl values (winning wound Oxyester EP-T568) joins in reactor, at the temperature of 110 ℃, vacuumize dehydration 2 hours, be cooled to below 40 ℃, add 17.8g isophorone diisocyanate, 0.1 gram of dibutyl tin laurate, 60 ℃ of reactions 2.8 hours, add successively 0.25 gram of MEHQ, 0.25 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 8.2 grams of senecioate-hydroxypropyl acrylates, continuation was 70 ℃ of reactions 2 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 39g acryloyl morpholine, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU3].
48g polymerization of acrylic modified polyurethane resin [AU3], 3g methacrylic ester modified liquid paracril (the Hypro 1300X43LC of CVC company), 26g Special Ring olefin acrylate monomer, 5g vinylformic acid-4-hydroxyl butyl ester, the EDTA-4Na aqueous solution of 0.05g10% concentration, 3.2g fumed silica (TS720 of Cabot Co.,Ltd) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2 hours, system is mixed; Then add 1g1-hydroxyl-cyclohexyl phenyl ketone, 1g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 0.8g γ-methacryloxypropyl trimethoxy silane and 0.05g pyrogallol, continue to stir 1 hour vacuumizing and defoaming, discharging.
Embodiment 4
The polyester diol that is 215 by 100 grams of hydroxyl values (winning wound Oxyester EP-HS2272) joins in reactor, at the temperature of 115 ℃, vacuumize dehydration 1 hour, be cooled to below 40 ℃, add 38.5 gram 4, 4'-diphenylmethanediisocyanate, 0.1 gram of dibutyl tin laurate, 65 ℃ of reactions 3 hours, add successively 0.3 gram of MEHQ, 0.45 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 19.5 grams of tertiary capric acid glycidyl ester acrylate, continuation was 75 ℃ of reactions 3 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 55g ethyl acrylate, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU4].
50 g polymerization of acrylic modified polyurethane resins [AU4], 5g methacrylic ester modified liquid paracril (the Hypro 1300X33LC of CVC company), 29g Special Ring olefin acrylate monomer, 6g Rocryl 410, the EDTA-Na aqueous solution of 0.06g10% concentration, 2.3g fumed silica (H20 of Wa Ke company) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2.5 hours, system is mixed; Then add 2g1-hydroxyl-cyclohexyl phenyl ketone, 3g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 1.2g γ-methacryloxypropyl trimethoxy silane and 0.05g pyrogallol, continue to stir 1.5 hours vacuumizing and defoaming, discharging.
Embodiment 5
The polyester diol that is 107 by 100 grams of hydroxyl values (winning wound Oxyester T1136) joins in reactor, at the temperature of 120 ℃, vacuumize dehydration 1.5 hours, be cooled to below 40 ℃, add 54.6 grams of xylylene diisocyanates, 0.1 gram of dibutyl tin laurate, 70 ℃ of reactions 2 hours, add successively 0.3 gram of MEHQ, 0.40 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 19.5 grams of tertiary capric acid glycidyl ester acrylate, continuation was 80 ℃ of reactions 2 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 25g2-phenoxyethyl acrylate, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU5].
52g polymerization of acrylic modified polyurethane resin [AU5], 7g methacrylic ester modified liquid paracril (the Hypro 1300X43LC of CVC company), 32g Special Ring olefin acrylate monomer, 7g 2-hydroxyl-3-benzene oxygen propyl group acrylate, the EDTA-2Na aqueous solution of 0.07g10% concentration, 3.4g fumed silica (R972 of Ying Chuan company) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2.5 hours, system is mixed; Then add 2g1-hydroxyl-cyclohexyl phenyl ketone, 2g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 1.5g γ-methacryloxypropyl trimethoxy silane and 0.08g pyrogallol, continue to stir 1.5 hours vacuumizing and defoaming, discharging.
Embodiment 6
The polyester diol that is 56 by 100 grams of hydroxyl values (winning wound Oxyester EP-T568) joins in reactor, at the temperature of 120 ℃, vacuumize dehydration 2 hours, be cooled to below 40 ℃, add 40.5 grams of xylylene diisocyanates, 0.1 gram of dibutyl tin laurate, 60 ℃ of reactions 2.5 hours, add successively 0.25 gram of MEHQ, 0.40 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 19.5 gram diethylene glycol monoacrylate, continuation was 65 ℃ of reactions 2.5 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 35g vinylformic acid ethoxy ethoxy ethyl ester, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU6].
55 g polymerization of acrylic modified polyurethane resins [AU6], 8g methacrylic ester modified liquid paracril (the Hypro 1300X33LC of CVC company), 36g Special Ring olefin acrylate monomer, 8g vinylformic acid caprolactone, the EDTA-3Na aqueous solution of 0.08g10% concentration, 4.3g fumed silica (TS530 of Cabot Co.,Ltd) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2.5 hours, system is mixed; Then add 1g1-hydroxyl-cyclohexyl phenyl ketone, 3g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 1.8g γ-methacryloxypropyl trimethoxy silane and 0.08g pyrogallol, continue to stir 1.8 hours vacuumizing and defoaming, discharging.
Embodiment 7
The polyester diol that is 215 by 100 grams of hydroxyl values (winning wound Oxyester EP-HS2272) joins in reactor, at the temperature of 110 ℃, vacuumize dehydration 1 hour, be cooled to below 40 ℃, add 36.8 grams of hexamethylene diisocyanates, 0.1 gram of dibutyl tin laurate, 65 ℃ of reactions 2.8 hours, add successively 0.2 gram of MEHQ, 0.3 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 26.8 grams of dipropylene glycol mono acrylic esters, continuation was 75 ℃ of reactions 3 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 48g lauryl acrylate, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU7].
58g polymerization of acrylic modified polyurethane resin [AU7], 9g methacrylic ester modified liquid paracril (the Hypro 1300X43LC of CVC company), 38g Special Ring olefin acrylate monomer, 4g methacrylic acid hydroxy butyl ester, 5g glycidyl methacrylate, the EDTA-4Na aqueous solution of 0.09g10% concentration, 4.8g fumed silica (R7200 of Ying Chuan company) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 3 hours, system is mixed; Then add 2g1-hydroxyl-cyclohexyl phenyl ketone, 1g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 2g γ-methacryloxypropyl trimethoxy silane and 0.1g pyrogallol, continue to stir 2.0 hours vacuumizing and defoaming, discharging.
Embodiment 8
The polyester diol that is 107 by 100 grams of hydroxyl values (winning wound Oxyester T1136) joins in reactor, at the temperature of 120 ℃, vacuumize dehydration 2 hours, be cooled to below 40 ℃, add 25.5 grams of hexamethylene diisocyanates, 0.1 gram of dibutyl tin laurate, 70 ℃ of reactions 3 hours, add successively 0.3 gram of MEHQ, 0.45 gram of oxidation inhibitor β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 11.5 gram 1, ammediol mono acrylic ester, continuation was 80 ℃ of reactions 3 hours, sampling is surveyed infrared spectra and is confirmed that the infrared absorption peak of isocyanate groups disappears, add 60g N, N DMAA, stir, cooling discharge is polymerization of acrylic modified polyurethane resin [AU8].
60g polymerization of acrylic modified polyurethane resin [AU8], 10g methacrylic ester modified liquid paracril (the Hypro 1300X33LC of CVC company), 40g Special Ring olefin acrylate monomer, 2g hydroxyethyl methylacrylate, 8g vinylformic acid-4-hydroxyl butyl ester, the EDTA-2Na aqueous solution of 0.1g10% concentration, 5.0g fumed silica (R8200 of Ying Chuan company) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 3 hours, system is mixed; Then add 3g1-hydroxyl-cyclohexyl phenyl ketone, 2g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 2g γ-methacryloxypropyl trimethoxy silane and 0.1g pyrogallol, continue to stir 2.0 hours vacuumizing and defoaming, discharging.
Comparative example
By 40g urethane acrylate oligomer (CN978 of Sartomer company), 20g modified epoxy acrylic ester (6215-100 of Changxing company), 30g vinylformic acid tetrahydrofuran ester, 20gN, N-DMAA, 7.1g fumed silica (R202 of Ying Chuan company) are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 3 hours, system is mixed; Then add 4g1-hydroxyl-cyclohexyl phenyl ketone, 1g2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, continues to stir 2.0 hours vacuumizing and defoaming, discharging.
The analytical test result of table 1 embodiment
Result shows, compares with comparative example, and the thixotropy modest viscosity of the ultraviolet cured adhesive that embodiment 1-8 obtains, and also after solidifying, anti-yellowing property is good, after harsh reliability testing, still can keep higher bonding strength, is applicable to the bonding of LED-backlit source lens.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a ultraviolet hardening structural adhesive, viscosity is 5000mPa.s～50000mPa.s, thixotropy index is 1.2～6, and described viscosity is according to GB/T 2794-1995, by Brookfield RV viscometer, tests the viscosity of glue sample under 25 ℃ of probe temperatures, 20rpm, described thixotropy index is according to GB/T 2794-1995, by Brookfield RV viscometer, test respectively glue sample at 25 ℃ of probe temperatures, viscosity under 2.5rpm and 20rpm, the ratio of the two is thixotropy index, it is characterized in that the raw material that contains following weight part: 40～60 parts of polymerization of acrylic modified polyurethane resins, 2～10 parts of methacrylic ester modified liquid paracrils, 20～40 parts of Special Ring olefin acrylate monomers, containing 2～10 parts of the acrylate of functional groups or methacrylate monomer, 1～5 part of light trigger, 1～5 part of fumed silica, 0.5～2 part of silane coupling agent, 0.01～0.1 part of pyrogallol, 0.001～0.01 part of stablizer, the structure following (I) of described Special Ring olefin acrylate monomer:
。
2. a kind of ultraviolet hardening structural adhesive as claimed in claim 1, described viscosity is 6000mPa.s～35000mPa.s, thixotropy index is 1.5～5.
3. the method for preparing a kind of ultraviolet hardening structural adhesive described in claim 1, is characterized in that comprising following steps:
(1) polyester diol is vacuumized at 110 ℃～120 ℃ to dehydration 1～2 hour, then add successively vulcabond, catalyzer, and at 50～70 ℃ abundant stirring reaction 2～3 hours, add successively again stopper, oxidation inhibitor, hydroxy acryl acid ester and fully stir at the temperature of 60～80 ℃, continue reaction 2～3 hours, until the absorption peak of isocyanate groups disappears in the infrared spectra that taking-up sample is recorded, then add reactive thinner, stir, cooling discharge, obtains polymerization of acrylic modified polyurethane resin;
(2) aforesaid propylene acid esters modified polyurethane resin, methacrylic ester modified liquid paracril, Special Ring olefin acrylate monomer, the acrylate that contains functional groups or methacrylate monomer, stablizer, fumed silica are added in double-planet dynamic mixing still successively, opening revolution stirs and high speed dispersion, continue to stir 2～3 hours, system is mixed, then add light trigger, silane coupling agent and pyrogallol, continue to stir 1～2 hour, vacuumizing and defoaming, discharging.
4. the preparation method of a kind of ultraviolet hardening structural adhesive as claimed in claim 3, is characterized in that polyester diol in step (1): vulcabond: the mol ratio of hydroxy acryl acid ester is 1:1.2～2.0:0.4～2.0; Described catalyzer, stopper, oxidation inhibitor all respectively account for 0.1 ‰～1 ‰ of step (1) raw material total mass; Described reactive thinner accounts for 20%～50% of step (1) raw material total mass.
5. the preparation method of a kind of ultraviolet hardening structural adhesive as claimed in claim 3, is characterized in that the described polyester diol of step (1) is a kind of in the polydiethylene glycol adipate dibasic alcohol, poly adipate succinic acid ester dibasic alcohol, poly-hexanodioic acid compound polyhydric alcohol ester dibasic alcohol series, polycaprolactone dibasic alcohol, PCDL, fatty acid modified polyester diol of molecular weight 500～3000; Described vulcabond is tolylene diisocyanate, 4, a kind of in 4-diphenylmethanediisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate; Described hydroxy acryl acid ester is senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, senecioate-hydroxy butyl ester, tertiary capric acid glycidyl ester acrylate, diethylene glycol monoacrylate, dipropylene glycol mono acrylic ester, 1, a kind of in ammediol mono acrylic ester, BDO mono acrylic ester; Described catalyzer is dibutyl tin laurate; Stopper is MEHQ; Oxidation inhibitor is β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester; Described reactive thinner is a kind of in ethyl acrylate, 2-phenoxyethyl acrylate, vinylformic acid ethoxy ethoxy ethyl ester, lauryl acrylate, isobornyl acrylate, vinylformic acid tetrahydrofuran ester, N,N-DMAA, acryloyl morpholine or any several mixture.
6. the preparation method of a kind of ultraviolet hardening structural adhesive as claimed in claim 1 or a kind of ultraviolet hardening structural adhesive claimed in claim 3, is characterized in that Hypro 1300X33LC or the Hypro 1300X43LC of described methacrylic ester modified liquid paracril WeiCVC company; The described acrylate containing functional groups or methacrylate monomer are a kind of in hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, glycidyl methacrylate, vinylformic acid-4-hydroxyl butyl ester, 2-hydroxyl-3-benzene oxygen propyl group acrylate, vinylformic acid caprolactone or any several mixture; Described stablizer is a kind of in ethylenediamine tetraacetic acid (EDTA) (EDTA), disodium ethylene diamine tetraacetate (EDTA-2Na), trisodium EDTA (EDTA-3Na), tetrasodium ethylenediamine tetraacetate (EDTA-4Na), is mixed with the aqueous solution of 10% concentration during use; Described fumed silica is TS-720, the TS-530 of Cabot Co.,Ltd, a kind of or any several mixture in H18, the H20 of the R202 of Ying Chuan company, R972, R7200, R8200 He Wake company; Described pyrogallol structure following (II):
；
Described light trigger is the mixture of 1-hydroxyl-cyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester; Described silane coupling agent is γ-methacryloxypropyl trimethoxy silane.
7. the application of a kind of ultraviolet hardening structural adhesive as claimed in claim 1 in LED-backlit source lens is bonding.
8. the application of a kind of ultraviolet hardening structural adhesive as claimed in claim 7 in LED-backlit source lens is bonding, it is characterized in that concrete steps are as follows: by ultraviolet hardening binding agent by some glue or silk screen printing on PCB substrate, again LED-backlit source lens is positioned on ultraviolet hardening binding agent, then by uviolizing, makes adhesive cures.
9. the application of a kind of ultraviolet hardening structural adhesive as claimed in claim 8 in LED-backlit source lens is bonding, the material that it is characterized in that described lens is a kind of in glass, quartz, acrylic, polycarbonate; Described uviolizing energy is at 3000mJ/cm
2below.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532274.0A CN103555261B (en) | 2013-11-01 | 2013-11-01 | Ultraviolet curing adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310532274.0A CN103555261B (en) | 2013-11-01 | 2013-11-01 | Ultraviolet curing adhesive and preparation method thereof |
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| CN104177969A (en) * | 2014-07-30 | 2014-12-03 | 桐乡市正大涂料有限公司 | Environmental-friendly inner coating adhesive for LED lamp tube or lamp cover and preparation method of inner coating adhesive |
| WO2018008332A1 (en) | 2016-07-04 | 2018-01-11 | 昭和電工株式会社 | Radical-curable adhesive composition and adhesive |
| CN107936903B (en) * | 2017-09-26 | 2020-12-18 | 广州机械科学研究院有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
| CN111344374B (en) * | 2017-11-17 | 2021-08-03 | 昭和电工株式会社 | Radical-curable adhesive composition and adhesive |
| CN109021675B (en) * | 2018-08-17 | 2021-06-15 | 广州市红太电子科技有限公司 | PCB printing ink |
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| KR101142804B1 (en) * | 2010-03-19 | 2012-05-08 | 주식회사 신광화학산업 | Ultraviolet Hardening Polyurethane Adhesive Making Method |
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| US5883148A (en) * | 1996-08-22 | 1999-03-16 | Acheson Industries, Inc. | UV curable pressure sensitive adhesive composition |
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