CN104974709B - UV moisture dual-curing type acrylate pressure-sensitive adhesive and preparation method thereof - Google Patents
UV moisture dual-curing type acrylate pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN104974709B CN104974709B CN201510477397.8A CN201510477397A CN104974709B CN 104974709 B CN104974709 B CN 104974709B CN 201510477397 A CN201510477397 A CN 201510477397A CN 104974709 B CN104974709 B CN 104974709B
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Abstract
The invention provides a UV moisture dual-curing type acrylate pressure-sensitive adhesive and a preparation method thereof. The adhesive is prepared by mixing and polymerizing the following components step by step: a (methyl) butyl acrylate monomer and/or a (methyl) ethyl acrylate monomer, a (methyl) acrylic 2-hexyl acetate monomer, a (methyl) methyl acrylate monomer, an N-methylol acrylamide monomer and/or an N-methylol methyl acrylamide monomer, carbamate acrylate, a polyamide type thermoplastic elastomer, rosin resin, epoxy modified polyurethane copolymer and a photoinitiator. The pressure-sensitive adhesive provided by the invention can be particularly suitable for a process for adhering TP to a shell bracket in portable electronic equipment.
Description
Technical field
The invention is related to the synthetically prepared field of acrylate pressure-sensitive adhesive, and in particular to one kind is applied to electronic product
The double curing type acrylic acid of bonding, the especially portable equipment such as mobile phone, panel computer touch-screen (TP) the UV moisture Nian Jie with frame
Ester pressure-sensitive.
Background technology
In the mancarried electronic aid assembling process such as mobile phone, panel computer, TP is direct with the adhesive effect of outer casing stand
One of key factor of influence mobile phone operation use and maintenance efficiency.It is to use that current major part TP is bonding with outer casing stand
Foam rubber and PUR.As electronic equipment is increasingly to the development trend of giant-screen narrow frame, existing adhesive product is also more next
More expose it and apply upper limitation in electronic equipment bonding.The bonding frame that foam rubber needs is wider, typically no less than
1mm, and maintenance process cull is difficult to clear up；PUR making technology needs the processes such as heating, pressurize, it is necessary to special equipment, residual
The equally more difficult cleaning of glue.
Pressure sensitive adhesive (PSA) refers to the adhesive that adherend surface just can be easily adhered to the pressure of very little.
UV solidified pressure-sensitives are one of research and most widely used type in acrylatcs systems pressure-sensitive adhesive agent, because its is efficient, green
Color, electricity-saving lamp advantage are allowed to obtain the development of high speed.In terms of TP is bonding with outer casing stand, the application of pressure sensitive adhesive is less,
The adhesive technology of new development proposes a kind of TP shells bonding that mobile phone will be applied to cushion pressure sensitive adhesive tape, with easily cut film,
Narrow frame up to 0.5mm, buffering antidetonation, be easily assembled to and repair the features such as.But in actual application, pressure sensitive adhesive is on narrow side
The bonding force of frame, the stripping ability of maintenance process, the ageing-resistant ability being applied in electronic product etc. are required to further lifting.
Acrylate pressure-sensitive adhesive is typically made up of soft monomer, hard monomer, functional monomer and some function additives, these structures
There is different degrees of influence to the performance of final pressure sensitive adhesive into composition.During the performance improvement of pressure sensitive adhesive, particularly with
For TP is bonding with outer casing stand, while obtaining the pressure with integrated performance indexs such as good initial bonding strength, bonding force, holding powers
Quick glue product is the dreamboat for producing and studying, and the balance of this combination property is often difficult to reach, such as initial bonding strength compared with
Often molecular weight is relatively low for good acrylate polymer, to the wellability of matrix preferably, but its mechanical performance is good, cohesive force compared with
It is weak and hold sticky difference；Improve polymer molecular weight and be obtained in that preferable holding power and cohesive force, strengthen pressure sensitive adhesive toughness, but together
When can cause the reduction of initial bonding strength and peel strength again.How to reconcile each constituent of acrylate pressure-sensitive adhesive and its content, make
It is to widen it to apply the problem of urgent need to resolve in electronic equipment bonding field that it obtains preferable combination property.
The content of the invention
The invention is solution the problems of the prior art, there is provided a kind of double curing types of the good UV moistures of combination property
Acrylate pressure-sensitive adhesive, is particular enable to the technique for sticking of TP and outer casing stand suitable for mancarried electronic aid, with operation just
Prompt, narrow side adhesive strength high, antidetonation, it is ageing-resistant, for ease of maintenaince the advantages of.
The double curing type acrylate pressure-sensitive adhesives of UV moistures that the invention is provided, by including following components in parts by weight system
：(methyl) Butyl Acrylate Monomer and/or 30~50 parts of (methyl) Hexyl 2-propenoate monomer (a), (methyl) acrylic acid 2- second
20~40 parts of the own ester monomer (b) of base, 5~10 parts of (methyl) methacrylate monomer (c), N hydroxymethyl acrylamide monomer and/
Or 1~5 part of N- methylol methacrylamides monomer (d), 0.5~6 part of urethane acrylate (e), polyamide-based heat
1~20 part of thermoplastic elastic (f), 5~10 parts of rosin resin (g), 10~50 parts of epoxy modified polyurethane copolymer (h), light draw
1~10 part of hair agent (i).
The double curing type acrylate pressure-sensitive adhesives of the UV moistures are obtained by including following steps：
S1：Part (methyl) 2-EHA monomer (b) is mixed and prepolymerization with whole rosin resins (g),
Obtain the first prepolymer；
S2：Will part (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a), surplus (methyl)
2-EHA monomer (b), part urethane acrylate (e) mixing and prepolymerization, obtain the second prepolymer；
S3：By surplus (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a), whole (methyl)
It is methacrylate monomer (c), whole N hydroxymethyl acrylamide monomer and/or N- methylol methacrylamides monomer (d), remaining
Amount urethane acrylate (e), whole polyamide-type thermoplastics elastomer (f), whole epoxy modified polyurethane copolymers
H (), whole light trigger (i) mixing, obtain the first pre-composition；
S4：Sheet is made after above-mentioned first prepolymer, the second prepolymer and the first pre-composition are mixed, be polymerized instead
Should.
The step of above-mentioned S1, S2 and S3 without sequencing point, can sequentially be carried out in practical operation, while carry out,
Changing sequence carries out or intersects to carry out.
Wherein, the urethane acrylate (e) adds as activity diluting monomer, on the one hand can be to soft monomer
Prepolymerization system viscosity carry out good control, on the other hand can be with macromolecular components epoxy modified polyurethane copolymer
H () and polyamide-type thermoplastic elastomer (f) have more preferable compatibility, preferably dilution effect is played in the presence of the two is common
Really, and amino introducing make acrylate have reactivity higher, quickly promote during sheet-like article polymerisation
Enter the carrying out of cross-linking polymerization, additionally it is possible to promote the compatibility of polyamide-type thermoplastic elastomer (f) and acrylic polymer.
The reduction of system molecular weight is excessively easily caused due to activity diluting monomer or solidifies insufficient, therefore need to strictly control its consumption.
The urethane acrylate (e) is preferably carbamate propylene of the viscosity (25 DEG C) in below 10cps
Acid esters.
Wherein, polyamide-type thermoplastic elastomer (f) has good phase with epoxy modified polyurethane copolymer (h)
Capacitive, tensile strength, shock resistance and antidetonation and ageing-resistant performance can be improved in addition acrylate pressure-sensitive adhesive system,
The deficiency of epoxy modified polyurethane copolymer (h) flexible chain is made up, the cohesive strength of pressure sensitive adhesive and mechanical performance is carried
Height, temperature tolerance, anti-seismic performance, holding power and stripping residual performance are optimised.The polyamide-type thermoplastic elastomer
F () is preferably polyamide 6 based thermoplastic elastomer, the copolymer being more preferably alternatively formed by PA6, polyethers.
Wherein, the rosin resin adds system as tackifying resin, with other tackifying resins such as terpene resin compared to tool
There is more preferable compatibility, the wellability of pressure sensitive adhesive product can be improved, improve initial bonding strength, preferably hydrogenated rosin resin.
Wherein, epoxy modified polyurethane copolymer (h) on the one hand can be such that pressure sensitive adhesive continues after UV solidifications trigger
Moisture-curable is carried out, when UV underexposures or insufficient solidification, as long as just can persistently be carried out with humidity in air
Crosslinking curing, improves solidification effect；On the other hand, polyurethane has soft segment, it is possible to increase acrylate pressure sensitive adhesive it is flexible
Property, there is preferable improvement to initial bonding strength and anti-seismic performance.Polyurethane is modified using epoxy, poly- ammonia can be improved
The harmful effect of ester heat resistance difference, while also functioning to good improvement result to the performance of polyurethane color inhibition.
Epoxy modified polyurethane copolymer (h) is commercially available or is voluntarily prepared by disclosed method.Preferably by wrapping
Include following Material synthesis：The epoxy monoacrylate of aliphatic diisocyanate, dihydroxylic alcohols or polyalcohol, hydroxyl, three
Mol ratio be preferably (1~1.2)：1：(0.5~0.8).
Wherein, the epoxy monoacrylate of the hydroxyl is by acrylic acid and 1 ring of glycidyl ester epoxy resin
Oxygen groups are reacted by esterification by ring opening and obtained, and while acrylic double bond is remained, are introduced epoxide group and are formed hydroxyl.Institute
State glycidyl ester epoxy resin preferred viscosities (25 DEG C) and be not higher than 30000mPas, refractive index is not less than 1.3 asphalt mixtures modified by epoxy resin
Fat；Preferably o-phthalic acid diglycidyl ester.Epoxide group is introduced into polyurethane, the mechanical property of polyurethane is significantly improved
Can (including tensile strength etc.), water resistance be solvent resistance, improve the toughness of polymer segment, and esters epoxy resin energy
Epoxy resin enough than other classifications provides lower viscosity, adhesive strength higher and light transmittance higher；In addition, by
Acrylic acid is introduced in hydroxyl is generated simultaneously after the esterification by ring opening reaction of acrylic acid and epoxide group, is eliminated individually in acrylic acid
The step of introducing hydroxyl, simplifies preparation technology.
Wherein, the aliphatic diisocyanate is preferably IPDI (IPDI).Although its reaction is lived
Property is weaker compared with aromatic diisocyanate, but toxic hazard is small and is difficult yellowing, can exist with the hydroxyl of dihydroxylic alcohols or polyalcohol
Reacted under felicity condition complete.
The dihydroxylic alcohols or polyalcohol are preferably the polyethylene glycol of ethylene glycol, hexylene glycol or mean molecule quantity below 420,
With hydroxyl value higher, it is easy to be reacted with the aliphatic diisocyanate, and introduce the glycidol esters asphalt mixtures modified by epoxy resin
Fat.
Wherein, the light trigger (i) is the mixture of radical photoinitiator and cationic photoinitiator, the two
Preferred mol ratio is (1~1.5)：1.The radical photoinitiator can include 2- hydroxy-2-methyl -1- phenylacetones
(1173), 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone (907), 2- dimethylamino -2- benzyls -
1- [4- (4- morpholinyls) phenyl] -1- butanone (IHT-PI 910), 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) benzene
Base] one or more in -1- acetone (659)；The cationic photoinitiator is chosen on aromatic hydrocarbons the virtue cyclopentadienyl with carbonyl
Molysite, such as [cyclopentadiene-iron -2,5- dimethyl acetophenones] salt, with space charge force and water splitting higher, while
Also the solidification of moisture will not be triggered when triggering without UV in adhesive.
Further, in aforesaid propylene acid esters pressure sensitive adhesive composition objects system, the consumption of hard monomer (c) is preferably soft monomer
The 10%~20% of the total amount of (a) and (b).The consumption of polyamide-type thermoplastic elastomer (f) be preferably soft monomer (a) and
The 5%~10% of the total amount of (b), hard monomer (c) and functional monomer (d).The consumption of epoxy modified polyurethane copolymer (h) is excellent
Elect the 30%~50% of the total amount of soft monomer (a) and (b), hard monomer (c) and functional monomer (d) as.Carbamate propylene
The consumption of acid esters (e) is preferably soft monomer (a) and (b), hard monomer (c), functional monomer (d), polyamide-type thermoplastic elastomer
The 2%~4% of the total amount of (f) and epoxy modified polyurethane copolymer (h).
In the preparation process of the double curing type acrylate pressure-sensitive adhesives of the UV moistures, (methyl) Butyl Acrylate Monomer
And/or (methyl) Hexyl 2-propenoate monomer (a), (methyl) 2-EHA monomer (b), urethane acrylate
The substep of (e) add and polymerization process can when acrylate pressure-sensitive adhesive product obtain molecular weight distribution wider, initial bonding strength and
Peel strength is more sensitive to low-molecular-weight, and holding power is more sensitive to HMW, and molecular weight distribution wider can make
The above-mentioned performance for obtaining pressure sensitive adhesive is preferably balanced.
Preferably, the consumption of (methyl) 2-EHA monomer (b) is its total input amount in the step S1
50%~80%.
Preferably, (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a) in the step S2
Consumption is the 95%~99% of its total input amount.
Preferably, urethane acrylate (e) consumption is the 30%~40% of its total input amount in the step S2.
Further, first prepolymer, the viscosity of the second prepolymer are controlled to 3000~10000mPas.
Further, in the step S1, rosin resin (g) be (methyl) 2-EHA monomer (b) with it is poly-
Close reaction system viscosity and reach what is added during 2000~4500mPas.
Preferably, the first prepolymer, the second prepolymer be placed in after the completion of prepolymerization in step S1, S2 quiet at room temperature
Put stabilization more than 20h carries out step S4 again.
Wherein, step S1, S2, the polymerization of S4 can carry out polymerisation under ultraviolet light conditions again, and ultraviolet light is maximum
Wavelength is 250~400nm, 1~2mW/cm of intensity2.Further, in carrying out polymerization process under the ultraviolet light conditions,
A small amount of light sensitizer, preferably benzoin isobutyl ether can also be added in each step, addition is preferably polymerized no more than the step
The 0.05% of each component gross weight in step.
Wherein, the polymerization of step S1, S2 can also be gathered between 60~80 DEG C in the presence of polymerization initiator
Close reaction.The polymerization initiator can be azodiisobutyronitrile (AIBN) and/or dibenzoyl peroxide (BPO).It is described poly-
It is 0.5~1% of total monomer weight in the step to close consumption of the initiator in corresponding steps.
During " (methyl) Butyl Acrylate Monomer " refers to Butyl Acrylate Monomer, butylmethacrylate monomer in the present invention
One kind or their mixture；Similarly, (methyl) alkyl acrylate monomer, such as (methyl) Hexyl 2-propenoate monomer, (first
Base) 2-EHA monomer, (methyl) methacrylate monomer etc., refer to respectively corresponding alkyl acrylate monomer,
One kind or their mixture in alkyl methacrylate monomer.
The double curing type acrylate pressure-sensitive adhesives of UV moistures that the invention is provided, Shao's A hardness is just glued between 60~90
Power is not less than No. 14 balls, and holding power retention time under 23 DEG C, 1kg load and 60 DEG C, 3kg load is not less than 7 days, 180 °
Peel strength is not less than 10.5N/25mm, can more than 150 DEG C of heatproof, and more than 10h can be maintained not fall off at 100 DEG C, can remove
Go ability and ageing-resistant performance excellent, reached the well balanced of combination property, be particularly well-suited in mancarried electronic aid TP with
It is simple to operate the need for the technique for sticking of outer casing stand, it is with low cost, it is adaptable to industrial production.The UV moistures that the present invention is provided
Double curing type acrylate pressure-sensitive adhesive volatile substances are few, asepsis environment-protecting, also sustainable after UV solidifications to carry out moisture-curable, reduce
The insufficient poor attachment defect for causing of solidification, in the range of very narrow bonding, such as little as 0.5mm and following, it is also possible to provide
Good adhesive effect.
Specific embodiment
The invention is further described below.In order to describe conveniently, the equipment in the invention is omitted
The operating procedure or condition of necessary or routine, such as cleaning, purification, thermometric, control stir speed (S.S.), those skilled in the art can
According to arbitrarily being adjusted the need for reaction.Under conditions of not conflicting, the feature in the present invention program in each embodiment can
To be mutually combined.
Performance evaluation method of testing of the invention is as follows：
Shao's A hardness：Carried out according to GB/T531.1-2008 standards.
Initial bonding strength:Carried out according to GB/T4852-2002 standards, 30 ° of inclined-plane, sample helps rolling section 100mm, test section 100mm.
Holding power：Carried out with reference to GB/T4851-1998 standards, environmental condition is respectively：1kg load, T2- at T1-23 DEG C
3kg load at 60 DEG C.
180 ° of peel strengths：Carried out according to GB2792-1998 standards, peeling rate 300mm/min.
The ability of can remove：Actual measurement, 50mm × 50mm samples are attached in aluminium sheet, glass plate, PE plates, PVC board respectively, 2kg
Pressure roller is rolled three times, places 1h after constant temperature 1h in 150 DEG C of thermostats, and taking-up is cooled to room temperature, peels off manually, and observe residual
Colloid situation.
Temperature tolerance：Carried out with reference to GB/T4851-1998 standards, adhesive tape is recorded at 100 DEG C and completely falls off the time.
Resistance to ag(e)ing：Carried out with reference to GB/T17875-1999 standards, ageing oven temperature 70 C, humidity 80%, ageing time
One week, initial bonding strength, holding power, 180 ° of peel strengths are tested after being cooled to room temperature.
Embodiment 1
Hydroquinone monomethyl ether and o-phthalic acid diglycidyl ester are well mixed, and heating for dissolving, 85 DEG C are warming up to, to
The acrylic acid containing tetraethylammonium bromide is wherein added dropwise, is incubated, reaction to acid number stops less than 3mgKOH/g, obtains after completion of the reaction
Obtain the epoxy monoacrylate of hydroxyl.N2Under protection atmosphere, after hexylene glycol is dehydrated, it is added dropwise thereto contains two while stirring
The IPDI of dibutyl tin laurate, is heated to 60 DEG C of reaction 4h after completion of dropping, cool down after completion of the reaction
To room temperature, terminal isocyanate group oligomer is obtained；Then proceed to be added dropwise thereto the epoxy acrylic list of the hydroxyl for having prepared
Ester, is heated to 85 DEG C of reaction 3h after completion of dropping, stopping is heated and lowered the temperature；Then low-pressure distillation is carried out to products therefrom, is removed
After lower-molecular substance, epoxy modified polyurethane copolymer (h) needed for obtaining, cooling lucifuge storage.In said process, the different Buddhist
That ketone diisocyanate, hexylene glycol, the mol ratio of the epoxy monoacrylate of hydroxyl are 1.2:1:0.8, the ring of the hydroxyl
O-phthalic acid diglycidyl ester and acrylic acid mol ratio are 1 in oxypropylene acid monoester：1.2, the hydroquinone monomethyl ether consumption
For IPDI, hexylene glycol, the epoxy monoacrylate gross weight of hydroxyl 0.2%, the tetraethyl bromination
Ammonium consumption is the 0.5% of o-phthalic acid diglycidyl ester and acrylic acid gross weight, and dibutyl tin laurate consumption is for oneself
The 0.5% of glycol and IPDI gross weight.
25 parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers and 0.01 weight portion benzoin isobutyl ether are mixed, 75 DEG C are heated to,
The use of maximum wavelength is 250~400nm, 1~2mW/cm of intensity2Ultraviolet light source shines carry out polymerisation, mixture glues
7 parts by weight of hydrogenated rosin resins are added when degree reaches 3500~4500mPas and is stirred, continue to mix 2~4h, then room temperature
Standing stablizes 20~30h, obtains the first prepolymer, and viscosity is (25 DEG C) 7500~8500mPas.
By 22 weight parts of methacrylic acid butyl ester monomers, the own ester monomer of 22 parts by weight of acrylic acid, 1.5 weight portion carbamic acids
Ester acrylate (25 DEG C of viscosity 9cps), 15 parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers and 0.01 weight portion benzoin isobutyl ether are mixed
Close, be heated to 75 DEG C, the use of maximum wavelength is 250~400nm, 1~2mW/cm of intensity2Ultraviolet light source shines be polymerized
2~4h of reaction, is then stored at room temperature and stablizes 20~30h, obtains the second prepolymer, and viscosity is (25 DEG C) 6000~6500mPa
s。
By 1 weight parts of methacrylic acid butyl ester monomer, 10 parts by weight of acrylic acid methylmethacrylate monomers, 5 weight portion N- methylols third
Acrylamide monomer, 2.5 weight portion urethane acrylates, 8 weight parts of polyamide analog thermoplastic elastomer (Ubes
PAE600), 40 weight portions epoxy modified polyurethane copolymer obtained above, 6 weight portion 2- hydroxy-2-methyl -1- phenyl third
Ketone and 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone and [cyclopentadiene-iron -2,5- dimethyl benzenes
Ethyl ketone] phosphorus hexafluoride mixture (mol ratio 1:1), the mixing of 0.01 weight portion benzoin isobutyl ether, obtains the first pre-composition.
After above-mentioned the first prepolymer for preparing, the second prepolymer and the first pre-composition are sufficiently mixed, coat through electricity
In the BOPET film of dizzy treatment, and release liners are covered, roll slabbing, the use of maximum wavelength is then 250~400nm, intensity
1~2mW/cm210~120s of ultraviolet curing, obtain final product pressure sensitive adhesive product (P1) through cold front heavy rain to room temperature.
Embodiment 2
65 are warming up to after 5 parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers and 0.05 weight portion azodiisobutyronitrile are mixed
DEG C, stirred under 120rad/min rotating speeds and be passed through nitrogen, 10 parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers are then added dropwise thereto
With the mixture of 0.05 weight portion azodiisobutyronitrile, 0.05 weight portion azodiisobutyronitrile is added after completion of dropping, continued
2~4h of reaction, is cooled to room temperature discharging, obtains the first prepolymer, and viscosity is (25 DEG C) 7000~8000mPas.
By 10 weight parts of methacrylic acid butyl ester monomers, the own ester monomer of 10 parts by weight of acrylic acid, 1 weight portion carbamate
The mixing of acrylate (25 DEG C of viscosity 7cps), 5 parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers and 0.2 weight portion azodiisobutyronitrile
After be warming up to 65 DEG C, stirred under 120rad/min rotating speeds and be passed through nitrogen, 10 weight parts of methacrylic acid are then added dropwise thereto
Butyl ester monomer, the own ester monomer of 17.5 parts by weight of acrylic acid, 1 weight portion urethane acrylate (25 DEG C of viscosity 7cps), 10
The mixture of parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers and 0.2 weight portion azodiisobutyronitrile, adds 0.2 after completion of dropping
Weight portion azodiisobutyronitrile, 2~4h of sustained response is cooled to room temperature discharging, obtains the second prepolymer, and viscosity is (25 DEG C)
4000~5500mPas.
By the own ester monomer of 2.5 parts by weight of acrylic acid, 8 parts by weight of acrylic acid methylmethacrylate monomers, 5 weight portion N- hydroxymethyl, methyls third
Acrylamide monomer, 3 weight portion urethane acrylates, 9 weight parts of polyamide analog thermoplastic elastomer (Ubes
PAE601), epoxy modified polyurethane copolymer, 4 weight portion 2- methyl-2- (4- morpholinyls) obtained in 40 parts by weight of example 1-
1- [4- (methyl mercapto) phenyl] -1- acetone and 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone and [ring
Pentadiene-iron -2,5- dimethyl acetophenones] phosphorus hexafluoride mixture (mol ratio 1:1), 0.01 weight portion benzoin isobutyl ether is mixed
Close, obtain the first pre-composition.
After above-mentioned the first prepolymer for preparing, the second prepolymer and the first pre-composition are sufficiently mixed, coat through electricity
In the BOPET film of dizzy treatment, and release liners are covered, roll slabbing, the use of maximum wavelength is then 250~400nm, intensity
1~2mW/cm210~120s of ultraviolet curing, obtain final product pressure sensitive adhesive product (P2) through cold front heavy rain to room temperature.
Embodiment 3
30 parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers and 0.005 weight portion benzoin isobutyl ether are mixed, 75 DEG C are heated to,
The use of maximum wavelength is 250~400nm, 1~2mW/cm of intensity2Ultraviolet light source shines carry out polymerisation, mixture glues
7 parts by weight of hydrogenated rosin resins are added when degree reaches 3500~4500mPas and is stirred, continue to mix 2~4h, then room temperature
Standing stablizes 20~30h, obtains the first prepolymer, and viscosity is (25 DEG C) 6000-6500mPas.
By 10 weight parts of methacrylic acid butyl ester monomers, the own ester monomer of 18.5 parts by weight of acrylic acid, 1.5 weight portion amino first
Acid esters acrylate (25 DEG C of viscosity 9cps), 10 parts by weight of acrylic acid 2- ethyl hexyl acrylate monomers and 0.005 weight portion styrax fourth
Ether mixes, and is heated to 75 DEG C, the use of maximum wavelength is 250~400nm, 1~2mW/cm of intensity2Ultraviolet light source shines carry out
2~4h of polymerisation, is then stored at room temperature and stablizes 20~30h, obtain the second prepolymer, viscosity be (25 DEG C) 7500~
8000mPa·s。
By 1.5 weight parts of methacrylic acid butyl ester monomers, 7 parts by weight of acrylic acid methylmethacrylate monomers, 3 weight portion N- methylols third
Acrylamide monomer, 2.5 weight portion urethane acrylates, 5 weight parts of polyamide analog thermoplastic elastomer (Ubes
PAE600), 24 weight portions epoxy modified polyurethane copolymer purchased in market, 3 weight portion 2- hydroxy-2-methyl -1- phenylacetones and 2-
Methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone and [cyclopentadiene-iron -2,5- dimethyl acetophenones] six
It is fluorinated the mixture (mol ratio 1 of phosphorus:1), the mixing of 0.005 weight portion benzoin isobutyl ether, obtains the first pre-composition.
After above-mentioned the first prepolymer for preparing, the second prepolymer and the first pre-composition are sufficiently mixed, coat through electricity
In the BOPET film of dizzy treatment, and release liners are covered, roll slabbing, the use of maximum wavelength is then 250~400nm, intensity
1~2mW/cm210~120s of ultraviolet curing, obtain final product pressure sensitive adhesive product (P3) through cold front heavy rain to room temperature.
The performance indications of above-described embodiment products obtained therefrom are as shown in table 1 below.
Table 1
Claims (12)
1. a kind of double curing type acrylate pressure-sensitive adhesives of UV moistures, are obtained by including following components in parts by weight：(methyl) propylene
Acid butyl ester monomer and/or 30~50 parts of (methyl) Hexyl 2-propenoate monomer (a), (methyl) 2-EHA monomer (b)
20~40 parts, 5~10 parts of (methyl) methacrylate monomer (c), N hydroxymethyl acrylamide monomer and/or N- hydroxymethyl, methyls
1~5 part of acrylamide monomer (d), 0.5~6 part of urethane acrylate (e), polyamide-type thermoplastic elastomer (f) 1
~20 parts, 5~10 parts of rosin resin (g), 10~50 parts of epoxy modified polyurethane copolymer (h), 1~10 part of light trigger (i)；
Wherein, epoxy modified polyurethane copolymer (h) is by including following Material synthesis：Aliphatic diisocyanate, dihydroxylic alcohols
Or the epoxy monoacrylate of polyalcohol, hydroxyl；
The double curing type acrylate pressure-sensitive adhesives of the UV moistures are made by including following steps：
S1：Part (methyl) 2-EHA monomer (b) is mixed and prepolymerization with whole rosin resins (g), is obtained
First prepolymer；
S2：Will part (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a), surplus (methyl) propylene
Sour 2- ethyl hexyl acrylate monomers (b), part urethane acrylate (e) mixing and prepolymerization, obtain the second prepolymer；
S3：By surplus (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a), whole (methyl) propylene
Sour methylmethacrylate monomer (c), whole N hydroxymethyl acrylamide monomers and/or N- methylol methacrylamides monomer (d), surplus ammonia
Urethane acrylate (e), whole polyamide-type thermoplastic elastomer (f), whole epoxy modified polyurethanes copolymer (h),
Whole light trigger (i) mixing, obtain the first pre-composition；
S4：Sheet is made after above-mentioned first prepolymer, the second prepolymer and the first pre-composition are mixed, polymerisation is carried out；
Dividing without sequencing the step of above-mentioned S1, S2 and S3.
2. double curing type acrylate pressure-sensitive adhesives of UV moistures according to claim 1, it is characterised in that (methyl) acrylic acid
The consumption of methylmethacrylate monomer (c) is (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a) and (methyl) third
The 10%~20% of the total amount of olefin(e) acid 2- ethyl hexyl acrylate monomers (b).
3. double curing type acrylate pressure-sensitive adhesives of UV moistures according to claim 1, it is characterised in that described polyamide-based
The consumption of thermoplastic elastomer (TPE) (f) is (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a) and (first
Base) 2-EHA monomer (b), (methyl) methacrylate monomer (c) and N hydroxymethyl acrylamide monomer and/
Or the 5%~10% of the total amount of N- methylol methacrylamides monomer (d).
4. double curing type acrylate pressure-sensitive adhesives of UV moistures according to claim 1, it is characterised in that described epoxide modified
The consumption of polyurethane copolymer (h) is (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a) and (first
Base) 2-EHA monomer (b), (methyl) methacrylate monomer (c) and N hydroxymethyl acrylamide monomer and/
Or the 30%~50% of the total amount of N- methylol methacrylamides monomer (d).
5. double curing type acrylate pressure-sensitive adhesives of UV moistures according to claim 1, it is characterised in that the carbamic acid
The consumption of ester acrylate (e) is (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a) and (methyl)
2-EHA monomer (b), (methyl) methacrylate monomer (c), N hydroxymethyl acrylamide monomer and/or N- hydroxyls
Methyl methacrylamide monomer (d), polyamide-type thermoplastic elastomer (f) and epoxy modified polyurethane copolymer (h) it
The 2%~4% of total amount.
6. double curing type acrylate pressure-sensitive adhesives of UV moistures according to claim 1, it is characterised in that the carbamic acid
Ester acrylate (e) is urethane acrylate of the viscosity in below 10cps at 25 DEG C；The polyamide-type thermoplastic bullet
Gonosome (f) is polyamide 6 based thermoplastic elastomer.
7. double curing type acrylate pressure-sensitive adhesives of UV moistures according to claim 6, it is characterised in that described polyamide-based
Thermoplastic elastomer (TPE) (f) is the copolymer being alternatively formed by PA6, polyethers.
8. double curing type acrylate pressure-sensitive adhesives of UV moistures according to claim 1, it is characterised in that described epoxide modified
In polyurethane copolymer (h), aliphatic diisocyanate, dihydroxylic alcohols or polyalcohol, the epoxy monoacrylate of hydroxyl rub
You are than being (1~1.2)：1：(0.5~0.8).
9. the method for preparing the double curing type acrylate pressure-sensitive adhesives of the UV moistures as described in claim any one of 1-8, including it is following
The step of：
S1：Part (methyl) 2-EHA monomer (b) is mixed and prepolymerization with whole rosin resins (g), is obtained
First prepolymer；
S2：Will part (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a), surplus (methyl) propylene
Sour 2- ethyl hexyl acrylate monomers (b), part urethane acrylate (e) mixing and prepolymerization, obtain the second prepolymer；
S3：By surplus (methyl) Butyl Acrylate Monomer and/or (methyl) Hexyl 2-propenoate monomer (a), whole (methyl) propylene
Sour methylmethacrylate monomer (c), whole N hydroxymethyl acrylamide monomers and/or N- methylol methacrylamides monomer (d), surplus ammonia
Urethane acrylate (e), whole polyamide-type thermoplastic elastomer (f), whole epoxy modified polyurethanes copolymer (h),
Whole light trigger (i) mixing, obtain the first pre-composition；
S4：Sheet is made after above-mentioned first prepolymer, the second prepolymer and the first pre-composition are mixed, polymerisation is carried out；
Dividing without sequencing the step of above-mentioned S1, S2 and S3.
10. method according to claim 9, it is characterised in that (methyl) 2-EHA in the step S1
The consumption of monomer (b) is the 50%~80% of its total input amount；In the step S2 (methyl) Butyl Acrylate Monomer and/or
The consumption of (methyl) Hexyl 2-propenoate monomer (a) is the 95%~99% of its total input amount；Carbamate in the step S2
Acrylate (e) consumption is the 30%~40% of its total input amount.
11. methods according to claim 9, it is characterised in that first prepolymer, the viscosity control of the second prepolymer
It is 3000~10000mPas.
12. methods according to claim 9, it is characterised in that in the step S1, the rosin resin (g) is in (first
Base) 2-EHA monomer (b) and polymerization reaction system viscosity reaches what is added during 2000~4500mPas.
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| CN110373119B (en) * | 2019-07-19 | 2021-07-20 | 聚隆(福建)包装有限公司 | Environment-friendly modified starch adhesive for manufacturing corrugated board, high-performance environment-friendly corrugated board and manufacturing method thereof |
| CN111876107B (en) * | 2020-02-20 | 2021-09-17 | 杭州星华反光材料股份有限公司 | Epoxy polyurethane modified acrylic resin adhesive and preparation method and application thereof |
| CN112708354A (en) * | 2021-01-07 | 2021-04-27 | 镝普材料(深圳)有限公司 | Single-component ultraviolet and moisture dual-curing polyurethane hot melt adhesive and preparation method thereof |
| CN113045697B (en) * | 2021-02-04 | 2021-10-12 | 东莞市德聚胶接技术有限公司 | Modified acrylate oligomer and UV (ultraviolet) and moisture dual-curing pressure-sensitive adhesive |
| CN113088202A (en) * | 2021-04-16 | 2021-07-09 | 厦门韦尔通科技有限公司 | UV glue for protecting exposed aluminum layer of battery aluminum plastic film and use method thereof |
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