CN105754545A - Ultraviolet mixing solidifying adhesive for display and preparation method thereof - Google Patents
Ultraviolet mixing solidifying adhesive for display and preparation method thereof Download PDFInfo
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- CN105754545A CN105754545A CN201610265474.8A CN201610265474A CN105754545A CN 105754545 A CN105754545 A CN 105754545A CN 201610265474 A CN201610265474 A CN 201610265474A CN 105754545 A CN105754545 A CN 105754545A
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- mercaptan
- sulfur
- ultraviolet light
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- acrylate
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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
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Abstract
The invention provides an ultraviolet mixing solidifying adhesive for a display and a preparation method thereof.The ultraviolet mixing solidifying adhesive for the display is prepared from, by weight, 40-90 parts of polyurethane graft modification sulfur-containing epoxy monoacrylate with the grafting ratio being 50% or above, 10-45 parts of an activated thinner, 1-5 parts of a photoinitiator and 1-10 parts of a thermal curing agent.By adopting the technical scheme, the adhesive is cured with the mixture of ultraviolet light and heat, has the high bonding strength for glass base materials and the like, meanwhile has the high refractivity, can meet the requirement for adhesion fixation of optical components in the display, and can also solve the problem that an existing adhesive is low in refractive index and the like, wherein the refractive index of the adhesive is 1.50 or above.
Description
Technical field
The invention belongs to field of adhesive technology, particularly relate to a kind of mixing cured adhesive of display ultraviolet light and
Preparation method.
Background technology
The main organic and/or inorganic materials of optical material and organic (polymer) material two class.The refractive index of optical material is its optics
One of most important index of performance, has conclusive impact to materials application.Inorganic optical material (is commonly called as " optical glass ")
With a long history, kind is numerous, its refraction index nD=1.437-1.935, including colouless optical glass) color optical glass, resistance to
Radio optics glass, non-browning glass and optical quartz glass etc., be industrially widely used in the manufacture lens of optical instrument, rib
Mirror, speculum, window etc..Inorganic optical material refractive index selectable region is relatively wide, have the good light transmission of higher refractive index,
The performances such as good chemical resistance, wearability, resistance to water soak.But inorganic optical material there are disadvantages that, such as material itself
Fragility is very big, and the impact strength of material is the highest, easy fragmentation.
For overcoming the shortcoming of inorganic optical material, organic optical materials has obtained studying widely, develop and applying.And nothing
Machine optical material is compared, and organic optical materials has following outstanding advantages, such as good processability, it is possible to obtain micron order
Other fine structure, is suitably applied in the device of particular/special requirement, such as CD and diffraction grating；Molding mode is various, Ke Yigen
The needs of border application select suitable molding mode factually, greatly reduce difficulty of construction.Additionally, polymeric optical material is tough
The better mechanical properties such as property, shock resistance, service life length, safety coefficient higher.Also there is the little light weight of density, easily contaminate
Look etc. advantage.Certainly, organic optical materials is limited to the chemical constitution of polymer self, it may have refraction index is the highest, hard
Spend low, the shortcomings such as heat resistance, weatherability, wearability, solvent resistance, resistance to water soak are poor.
At present, the research of organic optical materials be concentrated mainly on polymethyl methacrylate, polystyrene, Merlon,
The preparation of optical plastic material, the machine-shapings such as poly-4-methyl-1-pentene, poly bis allyl diglycol two carbonic ester, polyamide
And in related application, these optical plastics do not possess active function groups, replace part mainly as matrix material (plastics) inorganic
Optical material is prepared the parts such as eyeglass, optical thin film, prism and is applied on the equipment such as LCD/LED display screen, optical instrument.
The production of LED and LCD display needs multiple optical material, owing to inorganic optical material has higher refractive power
Rate, therefore in display screen, upper and lower base plate is substantially all or uses inorganic optical material glass now, but, its structure also needs
Wanting the optical thin films such as polaroid, alignment film, optical filter, this kind of film is processed in employing organic optical materials (optical plastic)
Then there is bigger advantage.
In display screen production, the index of refraction of glass substrate used and optical thin film can accomplish more than 1.5, is entirely capable of
Meet the optical requirement of display screen.But in process of production, need adhesive to carry out between these glass substrate and optical thin films
Bonding, now frequently with some adhesive indexs of refraction all below 1.30, although bonding layer is the thinnest, but the splicing of low index of refraction
Layer still can affect the optical effect of display screen.Along with the requirement the highest to product quality, display screen is glue used in producing
Glutinous agent is also required to be high refractive power.
Summary of the invention
For above technical problem, the invention discloses a kind of mixing cured adhesive of display ultraviolet light and preparation thereof
Method, this adhesive, under ultraviolet-heat is mixing cured, has stronger adhesive strength to glass baseplate etc., has height simultaneously
Refractivity, refraction index >=1.50, the gluing of optics in display can be met and fix, it is also possible to solve existing adhesive folding
The defects such as optical index is low.
To this, the technical solution used in the present invention is:
A kind of mixing cured adhesive of display ultraviolet light, it component included and weight percentage number thereof be: grafting
Rate is the polyurethane grafted modified sulfur-bearing epoxy monoacrylate of more than 50%, 40～90 parts；Reactive diluent, 10～45 parts；Light
Initiator, 1～5 part；Thermal curing agents 1～10 parts.
As a further improvement on the present invention, the described mixing cured adhesive of display ultraviolet light includes component and
Parts by weight are: percent grafting is the polyurethane grafted modified sulfur-bearing epoxy monoacrylate of more than 50%, 60～80 parts；Activity is dilute
Release agent, 14～33 parts；Light trigger, 3～4 parts；Thermal curing agents 3～5 parts.
As a further improvement on the present invention, described reactive diluent is monofunctional diluent, difunctional diluent, three officials
The mixture of one or more in diluent can be rolled into a ball.
As a further improvement on the present invention, described monofunctional diluent is glycidyl acrylate, acrylic acid fourth
Ester, at least one in methyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, N-ethene pyrrole alkanone.
As a further improvement on the present invention, described difunctional diluent is O-phthalic acid diethylene glycol diacrylate
Ester, phthalic acid tripropylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, new penta 2
Alcohol diacrylate, ethoxylated neopentylglycol diacrylate, 1,6 hexanediol diacrylate, 1,4-butanediol two propylene
In acid esters, ethoxylated bisphenol a diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate at least one
Kind.
As a further improvement on the present invention, described trifunctional diluent is trimethylolpropane trimethacrylate, second
Epoxide trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate are at least
A kind of.
As a further improvement on the present invention, described light trigger be benzoin and its derivatives, benzil derivatives, two
Alkoxy benzene ethyl ketone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, benzophenone or heterocycle arone compounds
In at least one；Described thermal curing agents is ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, lignocaine third
The mixture of one or more in amine, aliphatic modified amine, aromatic amine, phthalic anhydride, dicyandiamide.
As a further improvement on the present invention, described light trigger is benzoin methyl ether, benzoin ethyl ether, the positive fourth of styrax
Ether, diphenylthanedione, Dialkoxy acetophenones, chloroacetophenone, benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-third
Ketone, 1-hydroxycyclohexyl phenyl ketone, 4-methyl benzophenone, 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2,
4,6-tri-methyl benzophenone, isopropyl thioxanthone, 2-chlorothiaxanthenone, 1-chloro-4-propoxyl group thioxanthone, 2,4-bis-
At least one in ethyl thioxanthone, 2,4,6-trimethylbenzoy-dipheny phosphine oxide.
As a further improvement on the present invention, the described mixing cured adhesive of display ultraviolet light uses following methods
Solidify: first solidify under ultraviolet light, be then heating and curing.
Use this technical scheme, prepare based on polyurethane grafted modified sulfur-bearing epoxy monoacrylate, first pass through purple
Outer Light lnduced Free Radicals solidifies, acrylic double bond energy Quick cross-linking solidification in adhesive system, is formed and sticks the preliminary of base material
Connecing, then under conditions of heating, the epoxide group in system realizes heat cure, improves bonding action further,
As a further improvement on the present invention, described percent grafting is the polyurethane grafted modified sulfur-bearing epoxy acrylic of more than 50%
Monoesters uses following methods step to prepare:
Step S1: synthesis sulfur-bearing epoxy monoacrylate segment；
Step S2: synthesis of polyurethane acrylate segment；
Step S3: in reaction vessel add step S1 synthesis sulfur-bearing epoxy monoacrylate segment and step S2 synthesis
Urethane acrylate segment, and add dibutyl tin dilaurate, wherein, account for gross mass 0.1～the dibutyl tin of 0.5%
Cinnamic acid tin, the addition of sulfur-bearing epoxy monoacrylate segment and urethane acrylate segment meets sulfur-bearing epoxy acrylate
Being 1:0.5～1 with-NCO group mol ratio, the mass percent shared by dibutyl tin dilaurate is 0.1～0.3%；60
～at 100 DEG C, react 3～6h, obtain percent grafting and control the urethane acrylate modification sulfur-bearing epoxy acrylic more than 50%
Monoesters resin.
Use this technical scheme, based on the sulfur-bearing height refractive power resin of Novel belt acrylic double bond and epoxide group,
Preparing the high mixing cured adhesive of refractive power ultraviolet light, it is solid that this adhesive can be used in display the gluing between each optical material
Fixed.
As a further improvement on the present invention, step S1 synthesis sulfur-bearing epoxy monoacrylate segment comprises the following steps:
Adding epoxychloropropane in reaction vessel, be heated with stirring to 50～90 DEG C, be subsequently adding two mercaptan, the addition of two mercaptan is full
Foot two mercaptan are 1:5～10 with the mol ratio of epoxychloropropane；The mass concentration being subsequently adding same volume is 15%-20% hydrogen-oxygen
Change sodium solution, stirring reaction 0.5～2h, after cooling, add ether and the distilled water of 2～5 times of volumes of 2～5 times of volumes, separate
Organic layer, is washed to neutrality, is dried with anhydrous magnesium sulfate, filters, and solvent is removed in decompression, obtains sulfur-bearing epoxy；Containing gained
Sulphur epoxy adds in reaction vessel, is heated with stirring to 90～130 DEG C, is subsequently adding and accounts for the catalysis that mass fraction is 0.1～1.0%
Agent N, N-dimethyl benzylamine and 0.1～the polymerization inhibitor MEHQ of 1.0%；Add acrylic or methacrylic acid, institute
State the sour addition of acrylic or methacrylic meeting epoxide group with acrylic acid mol ratio is 2:1；Continue reaction 2～6h,
During by the acid number≤3mgKOH/g of alkalimetric titration to system, obtain sulfur-bearing epoxy monoacrylate segment.
As a further improvement on the present invention, described two mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide
Ether, 1,6-ethanthiol, 2,5-dimercaptothiodiazole, 1, pungent two mercaptan of 8-, 1,2-dithioglycol, 1,3-dimercaptopropane, 1,
9-nonyl two mercaptan, 1,7-mercaptan in heptan two, 3,6-dioxy-1, at least one in pungent two mercaptan of 8-.
As a further improvement on the present invention, step S2 synthesis of polyurethane acrylate segment comprises the following steps: instead
Answer addition diisocyanate in container, be heated with stirring to 50～90 DEG C, then two mercaptan or dihydroxylic alcohols be added dropwise to two isocyanic acids
In ester, being added with dibutyl tin dilaurate in described two mercaptan or dihydroxylic alcohols, wherein, the addition of two mercaptan or dihydroxylic alcohols is full
The mol ratio of foot diisocyanate and two mercaptan or dihydroxylic alcohols is 2:1, and the mass percent shared by dibutyl tin dilaurate is
0.1～1.0%；After reaction 2～6h, toward reaction system in, addition is added with the hydroxy-ethyl acrylate of MEHQ, wherein,
It is 1～1.1:2 that the addition of hydroxy-ethyl acrylate meets the mol ratio of hydroxy-ethyl acrylate and diisocyanate, described to hydroxyl
Mass percent shared by base methyl phenyl ethers anisole is 0.1～1.0%；Reaction system is heated to 60～100 DEG C, continues reaction 2～5h,
One end must be arrived and have NCO group and urethane acrylate segment that the other end is acrylic double bond.
As a further improvement on the present invention, described diisocyanate is toluene di-isocyanate(TDI) (TDI), diphenyl methane
Diisocyanate (MDI), hexamethylene diisocyanate (HDI), IPDI (IPDI), dicyclohexyl methyl hydride
At least one in diisocyanate (HMDI), PPDI (PPDI)；
As a further improvement on the present invention, described two mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,
6-ethanthiol, 2,5-dimercaptothiodiazole, 1, pungent two mercaptan of 8-, 1,2-dithioglycol, 1,3-dimercaptopropane, 1,9-nonyl two
Mercaptan, 1,7-mercaptan in heptan two, 3,6-dioxy-1, at least one in pungent two mercaptan of 8-.
As a further improvement on the present invention, described dihydroxylic alcohols be polyether Glycols, polyester diol, propane diols, new penta
Glycol, BDO, 1, at least one in 6-hexylene glycol.
The invention also discloses the preparation method of a kind of mixing cured adhesive of display ultraviolet light as above, first
Polyurethane grafted modified sulfur-bearing epoxy monoacrylate is uniformly mixed with reactive diluent, be subsequently adding light trigger with
Thermal curing agents stirring at low speed is uniform, and vacuum vibration deaeration obtains the mixing cured adhesive of ultraviolet light.
Technical side's scheme of the present invention, combines the feature of ultraviolet light polymerization, the ultraviolet light polymerization body of single acrylate
System, has that curing rate is fast, initiator type and an advantage such as resin types is more, but cubical contraction after there is also solidification
Greatly, adhesive force and the shortcoming such as bonding action is limited.The mode using ultraviolet light polymerization to be combined with heat cure, can effectively play two kinds
The advantage of curing mode, can reduce the shrinkage factor of curing system simultaneously, improves bonding action.
The invention have the benefit that
Use technical scheme, the sulfur-containing group with high refractive property is introduced in acrylate structure, with
Shi Liyong synthetic technology, makes have photo curable acrylic double bond and heat-setting epoxy radicals in resin structure simultaneously
Group.After this resin is prepared with reactive diluent etc., after ultraviolet light irradiates, the double bond rapid curing in resin, to bases such as glass
Material provides preliminary cementability, makes the epoxide group curing reaction in system the most under the action of heat, due to epoxide group
Existence, reduce the double bond density in system, it is possible to reduce the cubical contraction of solidification process, solid in ultraviolet-heat mixing
Under change effect, adhesive has bonding action more higher than single ultraviolet light polymerization, and the bonding coat after solidifying has high folding
The characteristic of light, refraction index >=1.50；The gluing of optics in display can be met fix, it is also possible to solve existing adhesive
The defects such as refraction index is low.Can be applicable to the gluing of optics etc. in LCD/LED display fix.
Detailed description of the invention
Below the preferably embodiment of the present invention is described in further detail.
Embodiment 1
A kind of mixing cured adhesive of display ultraviolet light, it component included and parts by weight thereof are:
Percent grafting is the polyurethane grafted modified sulfur-bearing epoxy monoacrylate 72 of 70%
Glycidyl acrylate 6
1,4 butanediol diacrylate 8
Triethylene glycol diacrylate 6
2-hydroxy-2-methyl-1-phenyl-1-acetone 3
Aliphatic modified amine 5
Described percent grafting is that the preparation method of the polyurethane grafted modified sulfur-bearing epoxy acrylate of 70% is:
The first step, adds the epoxychloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 50 DEG C, adds 0.5mol
1,6-ethanthiol, add the 20%NaOH solution of about 300mL, stirring reaction 2h, be cooled to room temperature, add 3 times of volumes
Ether and the distilled water of 4 times of volumes, separate organic layer, be washed to neutrality, be dried with anhydrous magnesium sulfate, filter, decompression remove
Solvent, obtains sulfur-bearing epoxy；The sulfur-bearing epoxy weighing the above-mentioned synthesis of 0.3mol adds in 500mL there-necked flask, is heated with stirring to
110 DEG C, it is subsequently adding and accounts for the catalyst n that mass fraction is 0.8%, N-dimethyl benzylamine and the polymerization inhibitor para hydroxybenzene first of 0.6%
Ether；Add the acrylic acid of 0.3mol, continue reaction 4h, obtain sulfur-bearing epoxy monoacrylate segment 1.；
Second step, adds the toluene di-isocyanate(TDI) (TDI) of 1.0mol in the there-necked flask of 1000mL, is heated to 50 DEG C, and two
Butyl tin dilaurate tin joins the 1 of 0.5mol, 9-nonyl two mercaptan by the 1.0% of gross mass, is added dropwise to toluene di-isocyanate(TDI)
(TDI) in solution, after dripping off, continue reaction 6h, the hydroxy-ethyl acrylate of 0.5mol add the MEHQ of 0.6%,
Add above-mentioned reaction system, be warming up to 90 DEG C of reaction 2.5h, i.e. obtain one end band NCO group and the other end is acrylic double bond
Sulfur-containing polyurethane acrylate segment 2.；
1. 3rd step, add the sulfur-bearing epoxy monoacrylate of 0.2mol in the there-necked flask of 500mL, adds 0.14mol's
2. sulfur-containing polyurethane acrylate, adds the dibutyl tin dilaurate accounting for gross mass 0.1%, is heated at 80 DEG C reacting 3h, i.e.
Obtain the urethane acrylate modification sulfur-bearing epoxy monoacrylate resin that percent grafting is 70%.
The preparation method of the described mixing cured adhesive of display ultraviolet light is: be first 70% by the percent grafting of synthesis
Polyurethane grafted modified sulfur-bearing epoxy acrylate and glycidyl acrylate, 1,4 butanediol diacrylate, three second two
Alcohol diacrylate is uniformly mixed, and is subsequently adding light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone and heat cure
Agent aliphatic modified amine stirring at low speed is uniform, and vacuum vibration deaeration obtains the high mixing cured adhesive of refractive power ultraviolet light.
The adhesive obtained is coated on glass substrate, after ultraviolet-heat is mixing cured, tests its performance, detection
The adhesive adhesive strength of the present embodiment is 2.3MPa(compression shear strength), there are good alcohol resistance and resistance to water, refraction index is
1.5213。
Embodiment 2
A kind of mixing cured adhesive of display ultraviolet light, it component included and parts by weight thereof are:
Percent grafting is 100% polyurethane grafted modified sulfur-bearing epoxy monoacrylate 80
Hydroxy-ethyl acrylate 5
Propylene glycol diacrylate 6
Trimethylolpropane trimethacrylate 3
1-hydroxycyclohexyl phenyl ketone 3
Dicyandiamide 3
Described percent grafting is that the preparation method of 100% polyurethane grafted modified sulfur-bearing epoxy acrylate is:
The first step, adds the epoxychloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 65 DEG C, adds 0.6mol
2,5-dimercaptothiodiazole, add the 18%NaOH solution of about 300mL, stirring reaction 1h, be cooled to room temperature, add 3 times
The ether of volume and the distilled water of 3 times of volumes, separate organic layer, be washed to neutrality, be dried with anhydrous magnesium sulfate, filters, decompression
Remove solvent, obtain sulfur-bearing epoxy；The sulfur-bearing epoxy weighing the above-mentioned synthesis of 0.3mol adds in 500mL there-necked flask, and stirring adds
Heat to 115 DEG C, be subsequently adding and account for the catalyst n that mass fraction is 0.7%, N-dimethyl benzylamine and 0.9% polymerization inhibitor to hydroxyl
Methyl phenyl ethers anisole；Add the acrylic acid of 0.3mol, continue reaction 3.5h, obtain sulfur-bearing epoxy monoacrylate segment 1.；
Second step, adds the IPDI (IPDI) of 2.0mol in the there-necked flask of 1000mL, is heated to 75
DEG C, dibutyl tin dilaurate joins the 4 of 1mol, 4'-dimercapto diphenyl sulfide by the 0.5% of gross mass, is added dropwise to different Buddhist
In your ketone diisocyanate (IPDI) solution, after dripping off, continue reaction 4h, the hydroxy-ethyl acrylate of 1mol adds 0.4%
MEHQ, adds above-mentioned reaction system, is warming up to 85 DEG C of reaction 3h, i.e. obtains one end band NCO group and the other end is
The sulfur-containing polyurethane acrylate segment of acrylic double bond is 2.；
1. 3rd step, add the sulfur-bearing epoxy monoacrylate of 0.2mol in the there-necked flask of 500mL, adds containing of 0.2mol
2. sulphur urethane acrylate, adds the dibutyl tin dilaurate accounting for gross mass 0.3%, is heated at 75 DEG C reacting 4.5h, i.e.
Obtain the urethane acrylate modification sulfur-bearing epoxy monoacrylate resin that percent grafting is 100%.
The preparation method of the described mixing cured adhesive of display ultraviolet light is with embodiment 1.
The adhesive obtained is coated on glass substrate, tests its performance after ultraviolet-heat is mixing cured, detect this
Bright adhesive bonding action is 2.5MPa(compression shear strength), there are good alcohol resistance and resistance to water, refraction index is 1.5932.
Embodiment 3
A kind of mixing cured adhesive of display ultraviolet light, it component included and parts by weight thereof are:
Percent grafting is the polyurethane grafted modified sulfur-bearing epoxy monoacrylate 60 of 50%
Hydroxypropyl acrylate 5
PDDA 8
Ethoxylated neopentylglycol diacrylate 10
Ethoxylated trimethylolpropane triacrylate 10
Isopropyl thioxanthone 3
Diethylaminopropylamine 4
Described percent grafting is that the preparation method of the polyurethane grafted modified sulfur-bearing epoxy acrylate of 50% is:
The first step, adds the epoxychloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 60 DEG C, adds 0.6mol
, 4,4'-dimercapto diphenyl sulfide, add the 15%NaOH solution of about 300mL, stirring reaction 1h, be cooled to room temperature, add 4
The ether of times volume and the distilled water of 5 times of volumes, separate organic layer, be washed to neutrality, be dried with anhydrous magnesium sulfate, filters, subtracts
Pressure removes solvent, obtains sulfur-bearing epoxy；The sulfur-bearing epoxy weighing the above-mentioned synthesis of 0.4mol adds in 500mL there-necked flask, stirring
Be heated to 130 DEG C, be subsequently adding and account for the catalyst n that mass fraction is 0.6%, N-dimethyl benzylamine and 1.0% polymerization inhibitor to hydroxyl
Base methyl phenyl ethers anisole；Add the acrylic acid of 0.4mol, continue reaction 3h, obtain sulfur-bearing epoxy monoacrylate segment 1.；
Second step, adds the methyl diphenylene diisocyanate (MDI) of 2.0mol in the there-necked flask of 1000mL, is heated to 60
DEG C, dibutyl tin dilaurate, by the 0.8% of the gross mass polyether Glycols joining 1mol, is added dropwise to diphenyl methane two different
In cyanate (MDI) solution, after dripping off continue reaction 4.5h, in the hydroxy-ethyl acrylate of 1mol add 0.3% to hydroxyl
Methyl phenyl ethers anisole, adds above-mentioned reaction system, is warming up to 95 DEG C of reaction 2h, i.e. obtains one end band NCO group and the other end is acrylic acid
The urethane acrylate segment of ester double bond is 2.；
1. 3rd step, add the sulfur-bearing epoxy monoacrylate of 0.3mol in the there-necked flask of 500mL, adds .0.15mol's
2. sulfur-containing polyurethane acrylate, adds the dibutyl tin dilaurate accounting for gross mass 0.2%, is heated at 65 DEG C reacting 5h, i.e.
Obtain the urethane acrylate modification sulfur-bearing epoxy monoacrylate resin that percent grafting is 50%.
The preparation method of the described mixing cured adhesive of display ultraviolet light is with embodiment 1.
The adhesive obtained is coated on glass substrate, first passes through ultraviolet light polymerization, after being then heating and curing, test it
Performance, the adhesive bonding action of the detection present invention is 1.9MPa(compression shear strength), there are good alcohol resistance and resistance to water, refractive power
Index is 1.5051.
Comparative example 1
If percent grafting is relatively low during polyurethane grafted modified sulfur-bearing epoxy acrylate, adhesive bonding action also can be affected
With refraction index.
The adhesive of contrast, it component included and parts by weight thereof are:
Polyurethane grafted modified sulfur-bearing epoxy monoacrylate (graft modification rate less than 50%) 55
Hydroxy-ethyl acrylate 10
Propylene glycol diacrylate 8
Ethoxylated neopentylglycol diacrylate 10
Ethoxylated trimethylolpropane triacrylate 10
Isopropyl thioxanthone 3
Diethylaminopropylamine 4
The preparation method of described polyurethane grafted modified sulfur-bearing epoxy acrylate is:
The first step, adds the epoxychloropropane of 3mol in 1000mL there-necked flask, is heated with stirring to 60 DEG C, adds 0.6mol
, 4,4'-dimercapto diphenyl sulfide, add the 15%NaOH solution of about 300mL, stirring reaction 1h, be cooled to room temperature, add 4
The ether of times volume and the distilled water of 5 times of volumes, separate organic layer, be washed to neutrality, be dried with anhydrous magnesium sulfate, filters, subtracts
Pressure removes solvent, obtains sulfur-bearing epoxy；The sulfur-bearing epoxy weighing the above-mentioned synthesis of 0.4mol adds in 500mL there-necked flask, stirring
Be heated to 130 DEG C, be subsequently adding and account for the catalyst n that mass fraction is 0.6%, N-dimethyl benzylamine and 1.0% polymerization inhibitor to hydroxyl
Base methyl phenyl ethers anisole；Add the acrylic acid of 0.4mol, continue reaction 3h, obtain sulfur-bearing epoxy monoacrylate segment 1.；
Second step, adds the methyl diphenylene diisocyanate (MDI) of 2.0mol in the there-necked flask of 1000mL, is heated to 60
DEG C, dibutyl tin dilaurate, by the 0.8% of the gross mass polyether Glycols joining 1mol, is added dropwise to diphenyl methane two different
In cyanate (MDI) solution, after dripping off continue reaction 4.5h, in the hydroxy-ethyl acrylate of 1mol add 0.3% to hydroxyl
Methyl phenyl ethers anisole, adds above-mentioned reaction system, is warming up to 95 DEG C of reaction 2h, i.e. obtains one end band NCO group and the other end is acrylic acid
The urethane acrylate segment of ester double bond is 2.；
1. 3rd step, add the sulfur-bearing epoxy monoacrylate of 0.3mol in the there-necked flask of 500mL, adds 0.06mol's
2. sulfur-containing polyurethane acrylate, adds the dibutyl tin dilaurate accounting for gross mass 0.2%, is heated at 65 DEG C reacting 5h, i.e.
Obtain the urethane acrylate modification sulfur-bearing epoxy monoacrylate resin of graft modification rate 20%, graft modification rate 50% with
Under.
The preparation method of adhesive is with embodiment 1.
The adhesive obtained is coated on glass substrate, tests its performance after ultraviolet-heat is mixing cured, detect this
Bright adhesive bonding action is 1.4MPa(compression shear strength), there are good alcohol resistance and resistance to water, refraction index is 1.4783.
Comparative example 2
The most common display adhesive mostly is thermohardening type, and it component included and parts by weight thereof are:
Epoxy resin 70
Aliphatic mono-functional glycidyl ethers 5
Trifunctional glycidol ether 5
Difunctional glycidol ether 7
Dimer acid diglycidyl ether 5
Fatty amine thermal curing agents 8
Carry out being mixed to get adhesive by above-mentioned substance, adhesive is coated on glass substrate, after about 120 DEG C solidification 2-3h
Testing its performance, detection adhesive bonding action is 1.47MPa(compression shear strength), refraction index is 1.2879.
From the point of view of curing mode and test result, traditional display packaging plastic mostly is single thermohardening type, as will be at height
Temperature is lower long-time fixing and solidifies, and affects production efficiency, and its refraction index only has 1.2879.
Come by the test result of embodiment 1 ~ embodiment 3 and comparative example 1, comparative example 1 being carried out contrast
Seeing, the adhesive of the present invention has the advantage that
(1) owing to selecting modified resin and adjusting by controlling percent grafting and formula, adhesive of the present invention can be under ultraviolet light
Rapid curing (within 10s) provides preliminary bonding action, such adhesive tentatively to shape, it is not necessary to fixing can thermosetting again
Improving bonding action further, its bonding action is higher than common display heat cure adhesive.By controlling resin
Percent grafting, its bonding action typically can reach more than 1.9MPa, higher than about the 1.4MPa of common heat curing-type adhesive.
(2) present invention is by controlling percent grafting and containing methods such as S groups so that the index of refraction after adhesive solidification reaches
More than 1.5, the index of refraction of ordinary hot curable type adhesive to be significantly higher than, performance change is obvious, can apply to diopter
Require high display gluing field.
Above content is to combine concrete preferred embodiment further description made for the present invention, it is impossible to assert
Being embodied as of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. the mixing cured adhesive of display ultraviolet light, it is characterised in that: it component included and parts by weight thereof are:
Percent grafting is the polyurethane grafted modified sulfur-bearing epoxy monoacrylate of more than 50%, 40～90 parts；Reactive diluent, 10～45
Part；Light trigger, 1～5 part；Thermal curing agents 1～10 parts.
The mixing cured adhesive of display ultraviolet light the most according to claim 1, it is characterised in that: described display is used
Component and parts by weight thereof that the mixing cured adhesive of ultraviolet light includes are: percent grafting is the polyurethane grafted modification of more than 50%
Sulfur-bearing epoxy monoacrylate, 60～80 parts；Reactive diluent, 14～33 parts；Light trigger, 3～4 parts；Thermal curing agents 3～5
Part.
The mixing cured adhesive of display ultraviolet light the most according to claim 1, it is characterised in that: described activity dilution
Agent is the mixture of one or more in monofunctional diluent, difunctional diluent, trifunctional diluent；Wherein, institute
Stating monofunctional diluent is glycidyl acrylate, butyl acrylate, methyl acrylate, hydroxy-ethyl acrylate, acrylic acid
At least one in hydroxypropyl acrylate, N-ethene pyrrole alkanone；Described difunctional diluent is O-phthalic acid diethylene glycol dipropyl alkene
Acid esters, phthalic acid tripropylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, new penta
Omega-diol diacrylate, ethoxylated neopentylglycol diacrylate, 1,6 hexanediol diacrylate, 1,4-butanediol dipropyl
In olefin(e) acid ester, ethoxylated bisphenol a diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate at least
A kind of；Described trifunctional diluent is trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane three acrylic acid
Ester, pentaerythritol triacrylate, propoxylated glycerol triacrylate at least one.
The mixing cured adhesive of display ultraviolet light the most according to claim 1, it is characterised in that: described light trigger
For benzoin and its derivatives, benzil derivatives, Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acyl group
At least one in phosphine oxide, benzophenone or heterocycle arone compounds；Described thermal curing agents is ethylenediamine, divinyl three
Amine, triethylene tetramine, TEPA, diethylaminopropylamine, aliphatic modified amine, aromatic amine, phthalic anhydride, double cyanogen are double
The mixture of one or more in amine.
The mixing cured adhesive of display ultraviolet light the most according to claim 4, it is characterised in that: described light trigger
For benzoin methyl ether, benzoin ethyl ether, styrax n-butyl ether, diphenylthanedione, Dialkoxy acetophenones, chloroacetophenone,
Benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 4-methyl benzophenone, 2-hydroxyl
Base-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2,4,6-tri-methyl benzophenone, isopropyl thioxanthone, 2-chlorine thia
Anthrone, 1-chloro-4-propoxyl group thioxanthone, 2,4-diethyl thioxanthone, 2,4,6-trimethylbenzoy-dipheny aoxidize
At least one in phosphine.
The mixing cured adhesive of display ultraviolet light the most according to claim 1, it is characterised in that: described display
Following methods is used to solidify with the mixing cured adhesive of ultraviolet light: first to solidify under ultraviolet light, be then heating and curing.
7. according to the mixing cured adhesive of display ultraviolet light described in claim 1 ~ 6 any one, it is characterised in that: institute
Stating the polyurethane grafted modified sulfur-bearing epoxy monoacrylate that percent grafting is more than 50% uses following methods step to prepare:
Step S1: synthesis sulfur-bearing epoxy monoacrylate segment；
Step S2: synthesis of polyurethane acrylate segment；
Step S3: in reaction vessel add step S1 synthesis sulfur-bearing epoxy monoacrylate segment and step S2 synthesis
Urethane acrylate segment, and add dibutyl tin dilaurate, wherein, account for gross mass 0.1～the dibutyl tin of 0.5%
Cinnamic acid tin, the addition of sulfur-bearing epoxy monoacrylate segment and urethane acrylate segment meets sulfur-bearing epoxy acrylate
Being 1:0.5～1 with-NCO group mol ratio, the mass percent shared by dibutyl tin dilaurate is 0.1～0.3%；60
～at 100 DEG C, react 3～6h, obtain percent grafting and control the urethane acrylate modification sulfur-bearing epoxy acrylic more than 50%
Monoesters resin.
The mixing cured adhesive of display ultraviolet light the most according to claim 7, it is characterised in that: the synthesis of step S1 contains
Sulphur epoxy monoacrylate segment comprises the following steps: adds epoxychloropropane in reaction vessel, is heated with stirring to 50～90
DEG C, it being subsequently adding two mercaptan, it is 1:5～10 that the addition of two mercaptan meets the mol ratio of two mercaptan and epoxychloropropane；Then
The mass concentration adding same volume is 15%-20% sodium hydroxide solution, stirring reaction 0.5～2h, after cooling, adds 2～5 times
The ether of volume and the distilled water of 2～5 times of volumes, separate organic layer, be washed to neutrality, be dried with anhydrous magnesium sulfate, filters, subtracts
Pressure removes solvent, obtains sulfur-bearing epoxy；The sulfur-bearing epoxy of gained is added in reaction vessel, is heated with stirring to 90～130 DEG C, so
Rear addition accounts for the catalyst n that mass fraction is 0.1～1.0%, N-dimethyl benzylamine and 0.1～the polymerization inhibitor para hydroxybenzene of 1.0%
Methyl ether；Adding acrylic or methacrylic acid, the addition of described acrylic or methacrylic acid meets epoxide group and third
The mol ratio of olefin(e) acid is 2:1；Continue reaction 2～6h, during by the acid number≤3mgKOH/g of alkalimetric titration to system, obtain sulfur-bearing ring
Oxypropylene acid monoester segment；
Described two mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,6-ethanthiol, 2,5-dimercapto
Thiadiazoles, 1, pungent two mercaptan of 8-, 1,2-dithioglycol, 1,3-dimercaptopropane, 1,9-nonyl two mercaptan, 1,7-mercaptan in heptan two, 3,6-
Dioxy-1, at least one in pungent two mercaptan of 8-.
The mixing cured adhesive of display ultraviolet light the most according to claim 7, it is characterised in that: the synthesis of step S2 is poly-
Urethane acrylate segment comprises the following steps: adds diisocyanate in reaction vessel, is heated with stirring to 50～90 DEG C, so
After two mercaptan or dihydroxylic alcohols are added dropwise in diisocyanate, described two mercaptan or dihydroxylic alcohols are added with dibutyl tin cinnamic acid
Tin, wherein, it is 2:1 that the addition of two mercaptan or dihydroxylic alcohols meets the mol ratio of diisocyanate and two mercaptan or dihydroxylic alcohols, two
Mass percent shared by butyl tin dilaurate tin is 0.1～1.0%；After reaction 2～6h, add in reaction system and be added with
The hydroxy-ethyl acrylate of MEHQ, wherein, the addition of hydroxy-ethyl acrylate meets hydroxy-ethyl acrylate and two isocyanides
The mol ratio of acid esters is 1～1.1:2, and the mass percent shared by described MEHQ is 0.1～1.0%；By reactant
System is heated to 60～100 DEG C, continues reaction 2～5h, and must arrive one end has NCO group and the other end to be the poly-of acrylic double bond
Urethane acrylate segment；
Described diisocyanate is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), hexa-methylene two
Isocyanates (HDI), IPDI (IPDI), dicyclohexyl methyl hydride diisocyanate (HMDI), different to benzene two
At least one in cyanate (PPDI)；
Described two mercaptan are 2,4-dimercapto pyrimidine, 4,4'-dimercapto diphenyl sulfide, 1,6-ethanthiol, 2,5-dimercapto
Thiadiazoles, 1, pungent two mercaptan of 8-, 1,2-dithioglycol, 1,3-dimercaptopropane, 1,9-nonyl two mercaptan, 1,7-mercaptan in heptan two, 3,6-
Dioxy-1, at least one in pungent two mercaptan of 8-；
Described dihydroxylic alcohols be polyether Glycols, polyester diol, propane diols, neopentyl glycol, BDO, 1,6-hexylene glycol
In at least one.
10. a preparation method for the mixing cured adhesive of display ultraviolet light as claimed in claim 1, its feature exists
In: first polyurethane grafted modified sulfur-bearing epoxy monoacrylate is uniformly mixed with reactive diluent, is subsequently adding light and draws
Send out agent and thermal curing agents stirring at low speed is uniform, vacuum vibration deaeration, obtain the mixing cured adhesive of ultraviolet light.
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| CN111534269A (en) * | 2020-05-07 | 2020-08-14 | 苏州金枪新材料股份有限公司 | Two-component flexible acrylate structural adhesive for bonding liquid crystal screen and preparation method thereof |
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| CN110016144A (en) * | 2019-04-03 | 2019-07-16 | 深圳职业技术学院 | A kind of water solubility polyfunctional group resin and preparation method thereof |
| CN110016144B (en) * | 2019-04-03 | 2021-08-03 | 深圳职业技术学院 | Water-soluble polyfunctional resin and preparation method thereof |
| CN110016295A (en) * | 2019-04-09 | 2019-07-16 | 浙江国能科技有限公司 | A kind of optical cement of touch screen crack forming mechanism and its application |
| CN111534269A (en) * | 2020-05-07 | 2020-08-14 | 苏州金枪新材料股份有限公司 | Two-component flexible acrylate structural adhesive for bonding liquid crystal screen and preparation method thereof |
| CN114276539A (en) * | 2021-12-30 | 2022-04-05 | 北京林业大学 | Thiol-modified PAE resin cross-linking agent, modified protein adhesive and preparation method thereof |
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