CN110396390A - A kind of ultra-violet curing structural film adhesive and preparation method thereof - Google Patents
A kind of ultra-violet curing structural film adhesive and preparation method thereof Download PDFInfo
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- CN110396390A CN110396390A CN201910709862.4A CN201910709862A CN110396390A CN 110396390 A CN110396390 A CN 110396390A CN 201910709862 A CN201910709862 A CN 201910709862A CN 110396390 A CN110396390 A CN 110396390A
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The present invention relates to structural film adhesive fields, more particularly it relates to a kind of ultra-violet curing structural film adhesive and preparation method thereof.First aspect of the present invention provides a kind of ultra-violet curing structural film adhesive, by weight, the raw material for preparing of the ultra-violet curing structural film adhesive includes 20~40 parts of polyurethane acrylate prepolymers, 20~30 parts of acrylate monomers, 10~20 parts of flexible resins, 1~3 part of photoinitiator, 0.1~0.5 part of curing agent, 0.5~2 part of promotor；The raw material for preparing of the polyurethane acrylate prepolymer includes polyether Glycols, diisocyanate and hydroxy acryl acid ester monomer；The number-average molecular weight of the polyether Glycols is 1000~4000.Ultra-violet curing structural film adhesive provided by the invention has excellent mechanical property, storage stability, heat resistance and chemical-resistant, can meet the occasion of high-intensitive application requirement, is suitble to large-scale production.
Description
Technical field
The present invention relates to structural film adhesive fields, more particularly it relates to a kind of ultra-violet curing structural film adhesive and its system
Preparation Method.
Background technique
Structure glue intensity height, antistripping, impact resistance, construction technology are easy.For metal, ceramics, plastics, rubber, timber
Etc. bonding between same materials or non-same material, can partially instead of welding, the tradition connection shape such as rivet, be bolted
Formula.Faying face stress distribution is uniform, to part without heat affecting and deformation.Structure glue is widely used in engineering, is mainly used for structure
Reinforcing, anchoring, bonding, repairing of part etc.；As steel bonding, viscous carbon fiber, bar planting, crack strengthening, sealing, hole repair, railway spike are viscous
Patch, surfacecti proteon, concrete bonding etc..
Aerospace, steamer, needs to be glued load-carrying construction part with sqtructural adhesive in automotive field track vehicle
It connects, during actual use the experience complex working conditions such as high/low temperature and humidity alternating, vibration, salt fog, therefore sqtructural adhesive should be
It is kept under above-mentioned condition high-intensitive.Currently, thering is epoxy resin, span to come resinae and cyanic acid resinae structure glue in the market
Film can satisfy application requirement on mechanical strength, but product cure cycle is long, temperature tolerance and chemical-resistant are insufficient, on the one hand
Production efficiency is reduced, complicated storage and use environment on the other hand cannot be coped with.
Summary of the invention
For some problems existing in the prior art, first aspect of the present invention provides a kind of ultra-violet curing structure glue
Film, by weight, the raw material for preparing of the ultra-violet curing structural film adhesive includes 20~40 parts of polyurethane acrylate prepolymers,
20~30 parts of acrylate monomers, 10~20 parts of flexible resins, 1~3 part of photoinitiator, 0.1~0.5 part of curing agent, 0.5~2
Part promotor；The raw material for preparing of the polyurethane acrylate prepolymer includes polyether Glycols, diisocyanate and containing hydroxyl
Base acrylate monomer；The number-average molecular weight of the polyether Glycols is 1000~4000.
As a preferred solution of the present invention, the acrylate monomer includes two degree of functionality acrylate monomers and three
Degree of functionality acrylate monomer.
As a preferred technical solution of the present invention, the two degrees of functionality acrylate is 10 in 25 DEG C of dynamic viscosity
~15mPa.s；The three-functionality-degree acrylate monomer is 90~100mPa.s in 25 DEG C of dynamic viscosity.
As a preferred technical solution of the present invention, the two degrees of functionality acrylate monomer and three-functionality-degree acrylic acid
The weight ratio of ester monomer is (1~3): 1.
As a preferred technical solution of the present invention, contain cyano in the flexible molecular resin.
As a preferred technical solution of the present invention, cyano accounts for 20~30wt% in the flexible molecular resin.
As a preferred technical solution of the present invention, the polyurethane acrylate prepolymer, acrylate monomer with
And the weight ratio of flexible resin is (1~3): 1:(1~2.5).
As a preferred technical solution of the present invention, the inorganic filler includes nanometer calcium carbonate, titanium dioxide, gas phase
At least one of silica.
As a preferred technical solution of the present invention, the photoinitiator is selected from 2- hydroxyl -4 '-(2- hydroxy ethoxy) -
2- methyl phenyl ketone, methyl o-benzoylbenzoate, 2- isopropyl thioxanthone, 2,4,6- trimethylbenzoy-dipheny
The combination of phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, any one or more in methyl benzoylformate.
The second aspect of the present invention provides a kind of preparation method of ultra-violet curing structural film adhesive, the ultra-violet curing structure
The preparation method of glue film includes: that flexible resin is put into closed kneader, is plasticized 5~15 minutes under the conditions of 180~210 DEG C
Afterwards, polyurethane acrylate prepolymer, acrylate monomer, kneading mixing are put into, temperature is reduced to 40 DEG C to draw hereinafter, putting into light
Send out agent, curing agent, promotor, continue kneading mixing, entered in adhesive film machine by forced feed, through continuous moulding, patch release film,
It is collected in rolls after cross cutting, obtains structural film adhesive.
Compared with the prior art, the invention has the following beneficial effects:
Ultra-violet curing structural film adhesive provided by the invention has excellent mechanical property, storage stability, heat resistance and resistance to
Chemicals can meet the occasion of high-intensitive application requirement；The raw material that the present invention prepares ultra-violet curing structural film adhesive is cheap and easy to get,
Simple process is free of solvent, environment friendly and pollution-free, product storage and easy to use, suitable large-scale production.
Specific embodiment
Illustrate the present invention below by way of specific embodiment, but is not limited to specific examples presented below.
First aspect of the present invention provides a kind of ultra-violet curing structural film adhesive, by weight, the ultra-violet curing knot
Structure glue film prepare raw material include 20~40 parts of polyurethane acrylate prepolymers, 20~30 parts of acrylate monomers, 10~20
The flexible resin of part, 1~3 part of photoinitiator, 0.1~0.5 part of curing agent, 0.5~2 part of promotor.
In one embodiment, by weight, the raw material for preparing of the ultra-violet curing structural film adhesive includes 20~40
Part polyurethane acrylate prepolymer, 20~30 parts of acrylate monomers, 10~20 parts of flexible resins, 2~4 parts of plasticizer, 20
~40 parts of inorganic fillers, 1~3 part of photoinitiator, 0.1~0.5 part of curing agent, 0.5~2 part of promotor.
Preferably, by weight, the raw material for preparing of the ultra-violet curing structural film adhesive includes 20~40 parts of polyurethane third
Olefin(e) acid ester prepolymer, 20~30 parts of acrylate monomers, 10~20 parts of flexible resins, 3 parts of plasticizer, 30 parts of inorganic fillers, 1 part
Photoinitiator, 0.3 part of curing agent, 0.7 part of promotor.
Polyurethane acrylate prepolymer
Contain acrylate-functional groups and urethane bond in the molecule of polyurethane acrylate prepolymer, after solidification
Adhesive has high-wearing feature, adhesion strength, flexibility, high-peeling strength and the excellent resistance to low temperature and poly- third of polyurethane
The optical property and weatherability of olefin(e) acid ester brilliance, are a kind of radiation curing materials of high comprehensive performance.
Preferably, the polyurethane acrylate prepolymer prepare raw material include polyether Glycols, diisocyanate with
And hydroxy acryl acid ester monomer.
In one embodiment, the number-average molecular weight of the polyether Glycols is 1000~4000；It is highly preferred that described
The number-average molecular weight of polyether Glycols is 2500.
Number-average molecular weight: polymer is identical by chemical composition and the degree of polymerization equal homologous mixture does not form, i.e., by
The different high polymer of molecular chain length mixes composition.Generally use average molecular weight characterization bulk of molecule.By molecule amount
Statistical average, then referred to as number-average molecular weight, symbol are (Mn).
Preferably, the polyether Glycols are polyethylene glycol oxide ether glycol and/or polypropylene oxide ether glycol；More preferably
Ground, the polyether Glycols are polypropylene oxide ether glycol, and the polypropylene oxide ether glycol does not limit purchase producer especially
System.
In one embodiment, the diisocyanate includes toluene 2,4- diisocyanate, phenylene diisocyanate, 4,
4- methyl diphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, two isocyanide of phenylenedimethylidyne
At least one of acid esters；Preferably, the diisocyanate includes toluene 2,4- diisocyanate, the toluene 2, bis- isocyanide of 4-
Acid esters is not particularly limited purchase producer.
In one embodiment, the hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate and/or 4- hydroxybutyl
Acrylate；Preferably, the hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, and the hydroxy-ethyl acrylate is to purchase factory
Family is not particularly limited.
In one embodiment, the preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, 40~50 DEG C,
Reaction 3 hours；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.9~0.95, investment
Catalyst leads to nitrogen protection, and material temperature is controlled at 65~70 DEG C, reacted 4~6 hours, and measurement isocyanate group content is lower than
Polymerization inhibitor is added when 0.5wt%, and reaction was completed, obtains polyurethane acrylate prepolymer.
Preferably, the preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, mixing speed 60
~180 revs/min, material temperature is controlled at 40~50 DEG C, is reacted 3 hours, measures isocyanate group content；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.9~0.95, investment
0.08wt% catalyst leads to nitrogen protection, and 60~180 revs/min of mixing speed, material temperature controls the reaction 4~6 at 65~70 DEG C
Hour, polymerization inhibitor is added when being lower than 0.5wt% in measurement isocyanate group content, and reaction was completed, and it is poly- to obtain polyurethane acrylate prepolymer
Object.
It is further preferred that the preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, mixing speed
120 revs/min, material temperature is controlled at 45 DEG C, is reacted 3 hours, and isocyanate group content is measured, and it is i.e. whole to reaction to reach 1.8wt%
Point；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.95, investment
0.08wt% catalyst dibutyltin dilaurylate leads to nitrogen protection, and 120 revs/min of mixing speed, material temperature is controlled at 70 DEG C,
Hydroquinone polymerization inhibitor is added after reaction 5 hours, and reaction was completed, obtains polyurethane acrylate prepolymer.
In one embodiment, the molar ratio of the polyether Glycols and diisocyanate is 1:(1.1~2)；It is more excellent
The molar ratio of selection of land, the polyether Glycols and diisocyanate is 1:2.
Acrylate monomer
Acrylate is the general name of the esters of acrylic acid and its homologue.Important has methyl acrylate, acrylic acid
Ethyl ester, 2- methyl methacrylate and ethyl 2-methacrylate etc..Energy autohemagglutination is copolymerized with other monomers, is to prepare gluing
Agent, synthetic resin, specific rubber and plastics monomer.Acrylate monomer can be with as activated monomer in UV curing process
Directly participate in system solidification crosslinking.
In one embodiment, the acrylate monomer includes two degree of functionality acrylate monomers and three-functionality-degree third
Olefin(e) acid ester monomer；Preferably, the two degrees of functionality acrylate is 10~15mPa.s in 25 DEG C of dynamic viscosity；Three official
Energy degree acrylate monomer is 90~100mPa.s in 25 DEG C of dynamic viscosity；It is further preferred that the two degrees of functionality propylene
The weight ratio of acid ester monomer and three-functionality-degree acrylate monomer is (1~2): 1；It is highly preferred that the two degrees of functionality acrylic acid
Ester monomer and the weight ratio of three-functionality-degree acrylate monomer are 1.5:1.
Dynamic viscosity is also referred to as dynamic viscosity, absolute viscosity or simple viscosity, is defined as the ratio between stress and strain rate,
It is 1m that it, which is numerically equal to area,2At a distance of two plates of 1m, when being performed relative motion with the speed of 1m/s, because between existing for fluid
Internal friction caused by interacting.
What the two degrees of functionality acrylate monomer can be enumerated has 3- hydroxyl -2,2- dimethyl propyl -3- hydroxyl -2,2- diformazan
Base propyl ester and acrylate, tri (propylene glycol) diacrylate, dipropylene glycol diacrylate, zinn glutaric alcohol diacrylate
Ester, third oxidation zinn glutaric alcohol diacrylate etc.；What the three-functionality-degree acrylate monomer can be enumerated has trihydroxy methyl third
Alkane triacrylate, ethoxyquin trimethylol propane triacrylate, the third oxidation trimethylol propane triacrylate, glycerol propoxylate
Triacrylate, three (2- ethoxy) isocyanuric acid triacrylates etc..
In one embodiment, the two degrees of functionality acrylate monomer is tri (propylene glycol) diacrylate；Institute
Stating three-functionality-degree acrylate monomer is trimethylolpropane trimethacrylate；The tri (propylene glycol) diacrylate and three
Hydroxymethyl-propane triacrylate is not particularly limited purchase producer.
Hydrone can enter the inside of structural film adhesive to structure glue during storage, react, tie with facile hydrolysis group
Structure glue film is gradually degraded, and the filler in structural film adhesive can stay in the surface of structure glue in the form of a powder, affects structure glue
It uses.Applicant has found the viscosity to tri (propylene glycol) diacrylate and trimethylolpropane trimethacrylate in an experiment
Carrying out certain limitation can be improved the storage stability of structural film adhesive.Possible cause is tri (propylene glycol) diacrylate
Surface tension is low compared with trimethylolpropane trimethacrylate, and the lower tri (propylene glycol) diacrylate of surface tension to tie
The surface of structure adhesive curing glue film can reduce, while non-polar group methyl and methylene in tri (propylene glycol) diacrylate molecule
Base can also enable surface to reduce, to completely cut off moisture in air and material, increase storage stability.Two contractings 3 third
The viscosity of omega-diol diacrylate increases, and may reduce storage stability, the reason is that tri (propylene glycol) diacrylate is viscous
The increase of degree results in system viscosity increase, and mobility reduces, and affects crosslink density, while the increase of system viscosity, two contractings
Tripropylene glycol diacrylate is not easy to move to the surface of solidified glue film, and the surface energy of solidified glue film cannot be effectively reduced.Three hydroxyls
The viscosity of propane tri is lower than 90mPa.s, and trimethylolpropane trimethacrylate may be made to be easier to move to
System surface enables the surface of solidified glue film to increase, and the crosslink density of solidified glue film can also reduce, to reduce structure glue
The tensile strength of film；The viscosity of trimethylolpropane trimethacrylate is higher than 100mPa.s, may will increase system viscosity, influences
Crosslinking, while the increase of viscosity, the structure xanthan molecule for forming tridimensional network can coat carbon-carbon double bond, influence solid
Change the time.
It is found by the applicant that the weight ratio of tri (propylene glycol) diacrylate and trimethylolpropane trimethacrylate also can
The performance of structural film adhesive is had an impact.The too high levels of trimethylolpropane trimethacrylate influence the appearance of structural film adhesive,
Possible cause is the too high levels of trimethylolpropane trimethacrylate, and the speed for solidifying crosslinking can quickly, so as to cause structure
Adhesive curing shrinking percentage is excessive, and glue-line easily splits.Tri (propylene glycol) diacrylate too high levels, curing time can increase.
Flexible resin
Flexible resin refers to the good resin of flexibility.
What flexible resin can be enumerated has chlorosulfonated polyethylene, neoprene, nitrile rubber, styrene-butadiene-benzene second
Alkene copolymer, styrene-isoprene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer.
In one embodiment, contain cyano in the flexible molecular resin；Preferably, in the flexible molecular resin
Cyano accounts for 20~30wt%；It is further preferred that cyano accounts for 28wt% in the flexible molecular resin；It is highly preferred that described soft
Tough resin is nitrile rubber, and the nitrile rubber is not particularly limited purchase producer.
In one embodiment, the polyurethane acrylate prepolymer, acrylate monomer and flexible resin weight
Amount is than being (1~3): 1:(1~2.5).
The addition of polyurethane acrylate resin prepolymer improves structure glue film strength, and possible cause is polyurethane propylene
The long flexible chain provided in acid ester resin molecule when by external force can FREE TORSION to a certain extent, play stress point
Scattered effect, however must have certain limitation to the molecular weight of polyurethane acrylate resin soft segment, applicants have discovered that working as
For number-average molecular weight at 1000~4000, effect is preferable, and molecular weight is too low, and crosslink density is too high, and cohesive strength is too big, stress
Greatly, structure glue shows as brittleness, therefore intensity is lower.When soft segment molecular weight is excessive, the crosslink density of structure glue is reduced, hard section
Relative amount is reduced, and the rigidity of molecule segment is reduced, the strength reduction of structure glue.However the addition of polyurethane acrylate resin
So that the heat resistance of structural film adhesive is deteriorated, in order to change this situation, need to be added nitrile rubber to improve heat resistance.Fourth
For nitrile rubber with the addition of polyurethane acrylate resin so that curing rate is low, possible cause is polyurethane acrylate resin sheet
Body hard section is mutually separated with soft segment, causes performed polymer to move in solidification extremely difficult, due to the influence of molecule diffusion, structure glue
Curing rate it is slow.So that the curing rate of structure glue reduces, possible cause is molecule in nitrile rubber for the addition of nitrile rubber
There is a large amount of-CN base on chain, this unsaturated group of-CN can absorb certain ultraviolet light intensity in far ultraviolet region, lead to light
The decomposition rate of initiator is slack-off, and the solidification rate of structure glue is slack-off.Applicants have unexpectedly found that two degree of functionality acrylic acid are added
Curing rate is improved after ester monomer and three-functionality-degree acrylate monomer, possible cause is the increase of degree of functionality, and oxygen is more difficult
It internally spreads, oxygen inhibition is reduced, so that the probability of polymerization is got higher.Therefore polyurethane acrylate resin, nitrile rubber, propylene
Acid ester monomer interdependence, to improve the performance of structure glue.
From Molecular Design angle, polyurethane acrylate prepolymer, nitrile rubber and polyfunctionality third are compounded
Olefin(e) acid ester monomer can integrate the outstanding advantages of polyurethane, polyacrylate and nitrile rubber, obtain excellent in mechanical performance, heat resistance
And chemical-resistant.It is difficult to however, the curing cross-linking reaction of acrylic monomers has in complicated polymeric matrix system
Reliable and stable solidification rate out, it is therefore desirable to which accuracy controlling each component ratio is to reach Good All-around Property.
The applicant has found in an experiment, only when polyurethane acrylate prepolymer, acrylate monomer and butyronitrile
Rubber weight ratio is (1~3): 1:(1~2.5) when, the performance of structure glue can just be got well.When the content of polyurethane is excessive, structure
The strength reduction of glue, possible cause be multiphase from soft segment with hard section the cohesive strength of structure glue is become smaller, cause to stretch
Intensity and shear strength reduce, while hard segment content is excessive, and the interior rotation of strand becomes difficult, to influence to be crosslinked.When third
When olefin(e) acid ester monomer content is excessive, torque is reduced, and solidification rate slows down, and possible cause is the crosslinking that acrylate makes structure glue
Density is excessively high, and structure glue becomes fragile；Double bond increases, and dies down so that motion of matter ability is opposite in system, solidification rate is caused to reduce.
When nitrile rubber content is excessive, solidification rate is reduced, and possible cause is that excessive-CN base absorption ultraviolet light leads to solidification rate
Slow down, and the activity of acrylate monomer is not enough to the ultraviolet light of counteracting-CN base absorption ,-CN base is also possible to can be with polyurethane
C=O isopolarity group on acrylate and acrylate monomer forms hydrogen bond, and interaction between the two is reinforced, resistance
The movement speed for hindering other substances in system, influences curing rate.
Plasticizer
Plasticiser is the high molecular material auxiliary agent being widely used in industrial production, also known as plasticizer.It is all to be added to
The increased substance of polymer plastic can be made to be referred to as plasticiser in polymer material.The use of plasticiser can improve macromolecule material
The performance of material reduces production cost, improves productivity effect.Plasticizer is a kind of important chemical products additive, as auxiliary agent
It is widely used in the materials such as plastic products, concrete, plaster, cement, gypsum, cosmetics and cleaning agent, especially in polychlorostyrene
In vinyl plastics product, in order to increase the plasticity of plastics and improve the intensity of plastics, needs to add phthalic acid ester, contain
Amount is sometimes up to the 50% of product.The effect of plasticizer mainly weakens the secondary bond between molecular resin, increases molecular resin key
Mobility, reduce the crystallinity of molecular resin, increase the plasticity of molecular resin, make its flexibility enhance, be easily worked, can
It is legal to be used for industrial use, it is widely present in food packaging, cosmetics, medical equipment and environment water.Such as it is fresh-keeping
Film, food packaging, toy etc..
In one embodiment, the plasticizer is dioctyl phthalate, the pungent nonyl ester of phthalic acid two, adjacent benzene
At least one of dioctyl phthalate diisodecyl ester；Preferably, the plasticizer is dioctyl phthalate, the phthalic acid two
Monooctyl ester is not particularly limited purchase producer.
Inorganic filler
Filler refers to the material being filled in other objects.In chemical engineering, filler refers to loaded on lazy in packed column
Property solid material, such as Pall ring and Raschig ring etc., effect is the contact surface for increasing solution-air, makes its mutually strong mixing.In
In chemical products, filler is also known as filler, refer to improve processing performance, Mechanical Properties of Products simultaneously (or) reduce consolidating for cost
Body material.
In one embodiment, the inorganic filler include nanometer calcium carbonate, titanium dioxide, in fumed silica extremely
Few one kind；Preferably, the inorganic filler includes nanometer calcium carbonate, titanium dioxide and fumed silica；Further preferably
Ground, the weight ratio of the nanometer calcium carbonate, titanium dioxide and fumed silica are (1~3): (1~3): 1；It is highly preferred that
The weight ratio of the nanometer calcium carbonate, titanium dioxide and fumed silica is 3:2:1；The nanometer calcium carbonate, titanium dioxide
Titanium and fumed silica are not particularly limited purchase producer.
Photoinitiator
Photoinitiator is also known as photosensitizer or light curing agent, is that one kind can be in ultraviolet region (250~420nm) or visible region
(400~800nm) absorbs the energy of certain wavelength, generates free radicals, cation etc., to cause monomer polymerization crosslinking curing
Compound.
In one embodiment, the photoinitiator include 2- hydroxyl -4 '-(2- hydroxy ethoxy) -2- methyl phenyl ketone,
Methyl o-benzoylbenzoate, 2- isopropyl thioxanthone, 2,4,6- trimethylbenzoy-dipheny phosphine oxide, 2,4,6-
At least one of trimethylbenzoyl phenyl phosphinic acid ethyl ester, methyl benzoylformate；Preferably, the photoinitiator includes benzene
Formic acid methyl esters；The methyl benzoylformate is not particularly limited purchase producer.
Curing agent
Curing agent also known as curing agent, curing agent or set agent are a kind of substance promoted or control curing reaction or mixing
Object.Resin solidification is chemically reacted by condensation, closed loop, addition or catalysis etc., makes thermosetting resin that irreversible variation occur
Process, solidification are to solidify and (be crosslinked) agent by addition to complete.Curing agent is essential additive, is either bonded
Agent, coating, castable all need addition curing agent, and otherwise epoxy resin cannot solidify.Mechanics of the kind of curing agent to solidfied material
Performance, heat resistance, water resistance, corrosion resistance etc. all have a significant impact.
What curing agent can be enumerated has alkali metal salt, amine carboxylate, quaternary amine and alkali metal salt of ammonium carboxylic acid of carboxylic acid etc..
In one embodiment, the curing agent includes powder-sulphur, and the powder-sulphur does not make spy to purchase producer
It does not limit.
Promotor
Promotor and catalyst or curing agent and used time, a kind of less substance of dosage of reaction rate can be improved.
In one embodiment, the promotor includes zinc oxide and/or magnesia；Preferably, the promotor packet
Include zinc oxide；The zinc oxide is not particularly limited purchase producer.
The second aspect of the present invention provides a kind of preparation method of ultra-violet curing structural film adhesive, the ultra-violet curing structure
The preparation method of glue film includes: that flexible resin is put into closed kneader, is plasticized 5~15 minutes under the conditions of 180~210 DEG C
Afterwards, polyurethane acrylate prepolymer, acrylate monomer, kneading mixing are put into, temperature is reduced to 40 DEG C to draw hereinafter, putting into light
Send out agent, curing agent, promotor, continue kneading mixing, entered in adhesive film machine by forced feed, through continuous moulding, patch release film,
It is collected in rolls after cross cutting, obtains structural film adhesive.
In one embodiment, the preparation method of the ultra-violet curing structural film adhesive includes: to throw in closed kneader
Enter flexible resin, after being plasticized 5~15 minutes under the conditions of 180~210 DEG C, puts into polyurethane acrylate prepolymer, acrylic acid
Ester monomer and inorganic filler, kneading mixing, temperature be reduced to 40 DEG C hereinafter, investment plasticizer, photoinitiator, curing agent, promotion
Agent continues kneading mixing, is entered in adhesive film machine by forced feed, collects in rolls after continuous moulding, patch release film, cross cutting,
Obtain structural film adhesive.
It is preferably carried out in mode in one kind, the preparation method of the ultra-violet curing structural film adhesive includes: in closed kneading
The flexible resin of investment setting proportion, is plasticized after ten minutes under the conditions of 180 DEG C in machine, the polyurethane propylene of investment setting proportion
Acid esters prepolymer, acrylate monomer and inorganic filler, kneading mixing 30 minutes, temperature was reduced to 25 DEG C, investment setting proportion
Plasticizer, photoinitiator, curing agent, promotor, continue kneading mixing 30 minutes after, adhesive film machine is entered by forced feed
In, it is collected in rolls after continuous moulding, patch release film, cross cutting, obtains structural film adhesive.
Embodiment
Hereinafter, the present invention is explained in more detail by embodiment, it should be appreciated that these embodiments are only
It is exemplary and not restrictive.If following example is raw materials used to be all commercially available without other explanations.
A: polyurethane acrylate prepolymer
A1: polyurethane acrylate prepolymer
The raw material for preparing of the polyurethane acrylate prepolymer includes polyether Glycols, diisocyanate and hydroxyl
Acrylate monomer；The polyether Glycols are polypropylene oxide ether glycol, number-average molecular weight 2500, purchased from Shandong blue star east
Big Co., Ltd, trade mark DL2000D；The diisocyanate is toluene 2, and 4- diisocyanate is purchased from DOW Chemical, the trade mark
For T-80；The molar ratio of the polyether Glycols and diisocyanate is 1:2；The hydroxy acryl acid ester monomer is acrylic acid
Hydroxyl ethyl ester is purchased from Jinan Ren Yuan Chemical Co., Ltd..
The preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, mixing speed
120 revs/min, material temperature is controlled at 45 DEG C, is reacted 3 hours, and isocyanate group content is measured, and it is i.e. whole to reaction to reach 1.8wt%
Point；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.95, investment
0.08wt% catalyst dibutyltin dilaurylate leads to nitrogen protection, and 120 revs/min of mixing speed, material temperature is controlled at 70 DEG C,
Hydroquinone polymerization inhibitor is added after reaction 5 hours, and reaction was completed, obtains polyurethane acrylate prepolymer.
A2: polyurethane acrylate prepolymer
The raw material for preparing of the polyurethane acrylate prepolymer includes polyether Glycols, diisocyanate and hydroxyl
Acrylate monomer；The polyether Glycols are polypropylene oxide ether glycol, and number-average molecular weight 1000 is purchased from Hubei Yong Kuo section
Skill Co., Ltd；The diisocyanate is toluene 2, and 4- diisocyanate is purchased from DOW Chemical, trade mark T-80；It is described poly-
The molar ratio of ether dihydric alcohol and diisocyanate is 1:2；The hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, purchased from Ji
Nan Renyuan Chemical Co., Ltd..
The preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, mixing speed
120 revs/min, material temperature is controlled at 45 DEG C, is reacted 3 hours, and isocyanate group content is measured, and it is i.e. whole to reaction to reach 1.8wt%
Point；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.95, investment
0.08wt% catalyst dibutyltin dilaurylate leads to nitrogen protection, and 120 revs/min of mixing speed, material temperature is controlled at 70 DEG C,
Hydroquinone polymerization inhibitor is added after reaction 5 hours, and reaction was completed, obtains polyurethane acrylate prepolymer.
A3: polyurethane acrylate prepolymer
The raw material for preparing of the polyurethane acrylate prepolymer includes polyether Glycols, diisocyanate and hydroxyl
Acrylate monomer；The polyether Glycols are polypropylene oxide ether glycol, and number-average molecular weight 4000 is purchased from Hubei Yong Kuo section
Skill Co., Ltd；The diisocyanate is toluene 2, and 4- diisocyanate is purchased from DOW Chemical, trade mark T-80；It is described poly-
The molar ratio of ether dihydric alcohol and diisocyanate is 1:2；The hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, purchased from Ji
Nan Renyuan Chemical Co., Ltd..
The preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, mixing speed
120 revs/min, material temperature is controlled at 45 DEG C, is reacted 3 hours, and isocyanate group content is measured, and it is i.e. whole to reaction to reach 1.8wt%
Point；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.95, investment
0.08wt% catalyst dibutyltin dilaurylate leads to nitrogen protection, and 120 revs/min of mixing speed, material temperature is controlled at 70 DEG C,
Hydroquinone polymerization inhibitor is added after reaction 5 hours, and reaction was completed, obtains polyurethane acrylate prepolymer.
A4: polyurethane acrylate prepolymer
The raw material for preparing of the polyurethane acrylate prepolymer includes polyether Glycols, diisocyanate and hydroxyl
Acrylate monomer；The polyether Glycols are polypropylene oxide ether glycol, and number-average molecular weight 600 is purchased from Hubei Yong Kuo section
Skill Co., Ltd；The diisocyanate is toluene 2, and 4- diisocyanate is purchased from DOW Chemical, trade mark T-80；It is described poly-
The molar ratio of ether dihydric alcohol and diisocyanate is 1:2；The hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, purchased from Ji
Nan Renyuan Chemical Co., Ltd..
The preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, mixing speed
120 revs/min, material temperature is controlled at 45 DEG C, is reacted 3 hours, and isocyanate group content is measured, and it is i.e. whole to reaction to reach 1.8wt%
Point；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.95, investment
0.08wt% catalyst dibutyltin dilaurylate leads to nitrogen protection, and 120 revs/min of mixing speed, material temperature is controlled at 70 DEG C,
Hydroquinone polymerization inhibitor is added after reaction 5 hours, and reaction was completed, obtains polyurethane acrylate prepolymer.
A5: polyurethane acrylate prepolymer
The raw material for preparing of the polyurethane acrylate prepolymer includes polyether Glycols, diisocyanate and hydroxyl
Acrylate monomer；The polyether Glycols are polypropylene oxide ether glycol, and number-average molecular weight 6000 is purchased from Hubei Yong Kuo section
Skill Co., Ltd；The diisocyanate is toluene 2, and 4- diisocyanate is purchased from DOW Chemical, trade mark T-80；It is described poly-
The molar ratio of ether dihydric alcohol and diisocyanate is 1:2；The hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, purchased from Ji
Nan Renyuan Chemical Co., Ltd..
The preparation method of the polyurethane acrylate prepolymer includes below step:
(1) polyether Glycols and diisocyanate are put into reaction kettle by setting proportion, leads to nitrogen protection, mixing speed
120 revs/min, material temperature is controlled at 45 DEG C, is reacted 3 hours, and isocyanate group content is measured, and it is i.e. whole to reaction to reach 1.8wt%
Point；
(2) hydroxy acryl acid ester monomer is put into, control isocyanate group and hydroxyl molar ratio are 0.95, investment
0.08wt% catalyst dibutyltin dilaurylate leads to nitrogen protection, and 120 revs/min of mixing speed, material temperature is controlled at 70 DEG C,
Hydroquinone polymerization inhibitor is added after reaction 5 hours, and reaction was completed, obtains polyurethane acrylate prepolymer.
B: acrylate monomer
B1: tri (propylene glycol) diacrylate is 13mPa.s in 25 DEG C of dynamic viscosities, public purchased from Ai Jianmeng group
Department
B2: trimethylolpropane trimethacrylate is 90mPa.s in 25 DEG C of dynamic viscosities, public purchased from Ai Jianmeng group
Department
B3: trimethylolpropane trimethacrylate is 100mPa.s in 25 DEG C of dynamic viscosities, public purchased from Ai Jianmeng group
Department
B4: trimethylolpropane trimethacrylate is 116mPa.s in 25 DEG C of dynamic viscosities, is purchased from the graceful science and technology of Fox
(Beijing) Co., Ltd
B5: trimethylolpropane trimethacrylate is (30~40) mPa.s in 25 DEG C of dynamic viscosities, graceful purchased from Fox
Think chemical products Co., Ltd in scientific and technological (Beijing) Co., Ltd Chengdu auspicious one
C: plasticizer
C1: dioctyl phthalate is purchased from Nanjing Rong Ji Chemical Co., Ltd.
D: inorganic filler
D1: nanometer calcium carbonate is purchased from poly- thousand Chemical Co., Ltd. in Shanghai, model JQ
D2: titanium dioxide, purchased from Shanghai Ji to biochemical technology Co., Ltd
D3: fumed silica is purchased from the source Xiang Tan Jia Ye biotechnology
E: photoinitiator
E1: methyl benzoylformate is purchased from Ai Jianmeng group company
F: curing agent
F1: powder-sulphur
G: promotor
G1: zinc oxide
H: flexible resin
H1: nitrile rubber, the nitrile rubber cyano account for 28wt%, are purchased from U.S. ZEON chemical company
H2: nitrile rubber, the nitrile rubber cyano account for 21wt%, are purchased from U.S. ZEON chemical company
Examples 1 to 20 provides a kind of ultra-violet curing structural film adhesive, the ultra-violet curing structure glue that Examples 1 to 20 provides
The formula of film is shown in Table 1, and 0 formulation dosage of Examples 1 to 2 is in parts by weight.
The preparation method for the ultra-violet curing structural film adhesive that the Examples 1 to 20 provides includes: to throw in closed kneader
The nitrile rubber for entering setting proportion is plasticized after ten minutes under the conditions of 180 DEG C, the polyurethane acrylate prepolymer of investment setting proportion
Polymers, acrylate monomer and inorganic filler, kneading mixing 30 minutes, temperature was reduced to 25 DEG C, the plasticising of investment setting proportion
Agent, photoinitiator, curing agent, promotor are entered in adhesive film machine after continuing kneading mixing 30 minutes by forced feed, through even
It is collected in rolls after continuous moulding, patch release film, cross cutting, obtains structural film adhesive.
Table 1
Continued 1
| Embodiment | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| A1 | 35 | 22 | 30 | 20 | 35 | 20 | 30 | 30 | 30 | 30 |
| A2 | ||||||||||
| A3 | ||||||||||
| A4 | ||||||||||
| A5 | ||||||||||
| B1 | 15 | 15 | 9 | 21 | 15 | 13 | 15 | 15 | 20 | 5 |
| B2 | 10 | 10 | 6 | 14 | 10 | 7 | 5 | 20 | ||
| B3 | ||||||||||
| B4 | 10 | |||||||||
| B5 | 10 | |||||||||
| C1 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| D1 | 10 | 12 | 15 | 15 | 7.5 | 23 | 15 | 15 | 15 | 15 |
| D2 | 5 | 8 | 10 | 10 | 5 | 15 | 10 | 10 | 10 | 10 |
| D3 | 1 | 3 | 5 | 5 | 2.5 | 7.5 | 5 | 5 | 5 | 5 |
| E1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| F1 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| G1 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| H1 | 5 | 25 | 20 | 10 | 20 | 20 | 20 | 20 | 20 | |
| H2 | 10 |
Performance Evaluation
1. curing time: the curing time for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is according to GB/T 24147-
2009 standards are tested, and wherein light source is 365nm, irradiation intensity 6mW/cm2。
2. tensile strength: the tensile strength for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is according to GB/T 6329-
1996 standards are tested.
3. shear strength: the shear strength for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is according to GB/T 7124-
2008 standards are tested.
4. Shao's D hardness: Shao D hardness for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is according to GB/T 531.1-
2008 standards are tested.
5. vertical torque: the vertical torque for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is pulled using digital display torsion
Hand is tested, and is applied a rotary force outward by the lever arm perpendicular to binding face to operate, is recorded maximum when unsticking
Torque.
6. Storage period: the Storage period for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is according to GB/T 7123.2-
2002 standards are tested.
7. heat resistance: the heat resistance for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is according to GB/T 7124-2008
Standard sample preparation, sample are placed in the conservation rate for testing its shear strength in 80 DEG C after 1000 hours, and it is excellent that conservation rate, which is greater than 80%,
Different, conservation rate is qualification between 60~80%, and conservation rate is failure less than 60%.
8. chemical-resistant: the chemical-resistant for the ultra-violet curing structural film adhesive that Examples 1 to 20 provides is according to GB/T
7124-2008 standard carries out sample preparation, and sample immerses bath of glass, isopropanol, anti-icing fluid, hydraulic oil, machine oil, kerosene, 95# vapour respectively
Taken out after 1 minute in oil, test its shear strength conservation rate, conservation rate be greater than 80% be it is excellent, conservation rate is between 60~80%
For qualification, conservation rate is failure less than 60%.
2 the performance test results of table
From the test result of table 2 known to ultra-violet curing structural film adhesive provided by the invention have excellent mechanical property,
Storage stability, heat resistance and chemical-resistant can meet the occasion of high-intensitive application requirement；The present invention prepares ultra-violet curing knot
The raw material of structure glue film is cheap and easy to get, simple process, is free of solvent, environment friendly and pollution-free, product storage and easy to use, suitable big rule
The production of mould.
Example above-mentioned is merely illustrative, and is used to explain the present invention some features of the method.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the combined selection of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (10)
1. a kind of ultra-violet curing structural film adhesive, which is characterized in that by weight, the preparation of the ultra-violet curing structural film adhesive is former
Expect to include 20~40 parts of polyurethane acrylate prepolymers, 20~30 parts of acrylate monomers, 10~20 parts of flexible resins, 1~3
Part photoinitiator, 0.1~0.5 part of curing agent, 0.5~2 part of promotor；The polyurethane acrylate prepolymer prepares raw material
Including polyether Glycols, diisocyanate and hydroxy acryl acid ester monomer；The number-average molecular weight of the polyether Glycols is
1000~4000.
2. ultra-violet curing structural film adhesive according to claim 1, which is characterized in that the acrylate monomer includes two functions
Spend acrylate monomer and three-functionality-degree acrylate monomer.
3. ultra-violet curing structural film adhesive according to claim 2, which is characterized in that the two degrees of functionality acrylate is at 25 DEG C
Dynamic viscosity be 10~15mPa.s；The three-functionality-degree acrylate monomer 25 DEG C dynamic viscosity be 90~
100mPa.s。
4. ultra-violet curing structural film adhesive according to claim 3, which is characterized in that the two degrees of functionality acrylate monomer and
The weight ratio of three-functionality-degree acrylate monomer is (1~3): 1.
5. any one ultra-violet curing structural film adhesive according to claim 1~4, which is characterized in that the flexible molecular resin
In contain cyano.
6. ultra-violet curing structural film adhesive according to claim 5, which is characterized in that cyano accounts for 20 in the flexible molecular resin
~30wt%.
7. any one ultra-violet curing structural film adhesive according to claim 1~4, which is characterized in that the polyurethane acroleic acid
The weight ratio of ester prepolymer, acrylate monomer and flexible resin is (1~3): 1:(1~2.5).
8. any one of according to claim 1~4 ultra-violet curing structural film adhesive, which is characterized in that the inorganic filler includes
At least one of nanometer calcium carbonate, titanium dioxide, fumed silica.
9. any one ultra-violet curing structure glue according to claim 1~4, which is characterized in that the photoinitiator is selected from 2-
Hydroxyl -4 '-(2- hydroxy ethoxy) -2- methyl phenyl ketone, methyl o-benzoylbenzoate, 2- isopropyl thioxanthone, 2,4,6-
Trimethylbenzoy-dipheny phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, in methyl benzoylformate
The combination of any one or more.
10. a kind of preparation method of any one according to claim 1~9 ultra-violet curing structural film adhesive, which is characterized in that institute
The preparation method for stating ultra-violet curing structural film adhesive includes: that flexible resin is put into closed kneader, in 180~210 DEG C of conditions
After lower plasticizing 5~15 minutes, polyurethane acrylate prepolymer, acrylate monomer, kneading mixing are put into, temperature is reduced to 40
DEG C hereinafter, investment photoinitiator, curing agent, promotor, continue kneading mixing, entered in adhesive film machine by forced feed, through even
It is collected in rolls after continuous moulding, patch release film, cross cutting, obtains structural film adhesive.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683967A (en) * | 2021-03-10 | 2021-11-23 | 晶澜光电科技(江苏)有限公司 | Insulating adhesive and preparation method thereof |
| CN114456769A (en) * | 2022-03-10 | 2022-05-10 | 南通康尔乐复合材料有限公司 | UV-cured optical transparent adhesive suitable for full lamination of thick-frame liquid crystal display module and preparation method thereof |
-
2019
- 2019-08-02 CN CN201910709862.4A patent/CN110396390A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683967A (en) * | 2021-03-10 | 2021-11-23 | 晶澜光电科技(江苏)有限公司 | Insulating adhesive and preparation method thereof |
| CN114456769A (en) * | 2022-03-10 | 2022-05-10 | 南通康尔乐复合材料有限公司 | UV-cured optical transparent adhesive suitable for full lamination of thick-frame liquid crystal display module and preparation method thereof |
| CN114456769B (en) * | 2022-03-10 | 2023-06-09 | 南通康尔乐复合材料有限公司 | UV-cured optical transparent adhesive suitable for full lamination of thick-frame liquid crystal display module and preparation method thereof |
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