CN105754545B - A kind of display ultraviolet light mixing cured adhesive and preparation method thereof - Google Patents
A kind of display ultraviolet light mixing cured adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN105754545B CN105754545B CN201610265474.8A CN201610265474A CN105754545B CN 105754545 B CN105754545 B CN 105754545B CN 201610265474 A CN201610265474 A CN 201610265474A CN 105754545 B CN105754545 B CN 105754545B
- Authority
- CN
- China
- Prior art keywords
- added
- ultraviolet light
- mercaptan
- sulfur
- light mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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 present invention provides a kind of display ultraviolet light mixing cured adhesive and preparation method thereof, the component and its weight percentage that the ultraviolet light mixing cured adhesive of the display includes are as follows: its component for including and its weight percentage are as follows: the polyurethane grafted modified sulfur-bearing epoxy monoacrylate that grafting rate is 50% or more, 40~90 parts;Reactive diluent, 10~45 parts;Photoinitiator, 1~5 part;1~10 part of thermal curing agents.Using technical solution of the present invention, the adhesive is in the case where ultraviolet-heat is mixing cured, there is stronger adhesive strength to glass baseplate etc., there is high refractivity simultaneously, refraction index >=1.50, the gluing for being able to satisfy optical component in display is fixed, and also can solve the defects such as existing adhesive refraction index is low.
Description
Technical field
The invention belongs to field of adhesive technology more particularly to a kind of ultraviolet light mixing cured adhesive of display and its
Preparation method.
Background technique
The main organic and/or inorganic materials of optical material and organic two class of (polymer) material.The refractive index of optical material is its optics
One of most important index of performance has conclusive influence to material application.Inorganic optical material (is commonly called as " optical glass ")
With a long history, kind is numerous, refraction indexnD=1.437-1.935, including colouless optical glass) color optical glass, resistance to
Radio optics glass, non-browning glass and optical quartz glass etc. are industrially widely used in lens, the rib of manufacture optical instrument
Mirror, reflecting mirror, window etc..Inorganic optical material refractive index selectable region is wider, have the good translucency of higher refractive index,
The performances such as good chemical resistance, wearability, resistance to water soak.But there are some disadvantages, such as material itself for inorganic optical material
Brittleness is very big, and the impact strength of material is not high, easy to break.
The shortcomings that overcome inorganic optical material, organic optical materials have obtained extensive research, development and application.And nothing
Machine optical material is compared, and organic optical materials is good with following some outstanding advantages, such as processing performance, can obtain micron order
Other fine structure is suitably applied in the device of particular/special requirement, such as CD and diffraction grating;Molding mode multiplicity, Ke Yigen
Suitable molding mode is selected according to the needs of practical application, greatly reduces difficulty of construction.In addition, polymeric optical material is tough
Better mechanical properties, long service life, the safety coefficients such as property, shock resistance are higher.Also there is the small light weight of density, be easy dye
The advantages that color etc..Certainly, organic optical materials is limited to the chemical structure of polymer itself, it may have refraction index is not high, hard
Spend it is low, the disadvantages of heat resistance, weatherability, wearability, solvent resistance, poor resistance to water soak.
Currently, the research of organic optical materials be concentrated mainly on polymethyl methacrylate, polystyrene, polycarbonate,
Preparation, the machine-shaping of the optical plastics materials such as poly- 4-methyl-1-pentene, two carbonic ester of poly bis allyl diglycol, polyamide
And in related application, these optical plastics do not have active function groups, replace part inorganic mainly as basis material (plastics)
Optical material prepares the components such as eyeglass, optical thin film, prism and is applied in the equipment such as LCD/LED display screen, optical instrument.
The production of LED and LCD display needs a variety of optical materials, due to inorganic optical material refractive power with higher
Rate, therefore upper and lower base plate is substantially all now or is still also needed in structure using inorganic optical material glass in display screen
The optical thin films such as polaroid, alignment film, optical filter are wanted, this kind of film is processed using organic optical materials (optical plastic)
Then there is biggish advantage.
The index of refraction of glass substrate used in display screen production and optical thin film can accomplish 1.5 or more, be entirely capable of
Meet the optical requirement of display screen.But in process of production, adhesive is needed to carry out between these glass substrates and optical thin film
Bonding, although now frequently with some adhesive indexs of refraction all 1.30 hereinafter, bonding layer is very thin, the splicing of low index of refraction
Layer still will affect the optical effect of display screen.With to product quality increasingly higher demands, glue used in display screen production
Glutinous agent is also required to be high refractive power.
Summary of the invention
Against the above technical problems, the invention discloses a kind of display ultraviolet light mixing cured adhesive and its preparation
Method, which has stronger adhesive strength in the case where ultraviolet-heat is mixing cured, to glass baseplate etc., while having height
Refractivity, refraction index >=1.50, the gluing for being able to satisfy optical component in display are fixed, and also can solve existing adhesive folding
The defects such as optical index is low.
In this regard, the technical solution adopted by the present invention are as follows:
A kind of ultraviolet light mixing cured adhesive of display comprising component and its weight percentage number are as follows:
The polyurethane grafted modified sulfur-bearing epoxy monoacrylate that grafting rate is 50% or more, 40~90 parts;Reactive diluent, 10~45
Part;Photoinitiator, 1~5 part;1~10 part of thermal curing agents.
As a further improvement of the present invention, the ultraviolet light mixing cured adhesive of the display includes component and its
Parts by weight are as follows: the polyurethane grafted modified sulfur-bearing epoxy monoacrylate that grafting rate is 50% or more, 60~80 parts;Activity is dilute
Release agent, 14~33 parts;Photoinitiator, 3~4 parts;3~5 parts of thermal curing agents.
As a further improvement of the present invention, the reactive diluent be monofunctional diluent, difunctional diluent,
One or more of mixture in trifunctional diluent.
As a further improvement of the present invention, the monofunctional diluent is glycidyl acrylate, acrylic acid fourth
Ester, at least one of methyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, N- ethylene pyrrole alkanone.
As a further improvement of the present invention, the difunctional diluent is O-phthalic acid diethylene glycol diacrylate
Ester, phthalic acid tripropylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, new penta 2
Alcohol diacrylate, ethoxylated neopentylglycol diacrylate, 1,6 hexanediol diacrylate, two propylene of 1,4- butanediol
Acid esters, ethoxylated bisphenol a diacrylate, diethylene glycol diacrylate, at least one in triethylene glycol diacrylate
Kind.
As a further improvement of the present invention, the trifunctional diluent is trimethylolpropane trimethacrylate, second
Oxygroup trimethylolpropane trimethacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate are at least
It is a kind of.
As a further improvement of the present invention, the photoinitiator is 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
At least one of;The thermal curing agents are ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, lignocaine third
The mixture of one or more of amine, aliphatic modified amine, aromatic amine, phthalic anhydride, dicyandiamide.
As a further improvement of the present invention, the photoinitiator 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,
The chloro- 4- propoxyl group thioxanthone of 4,6- tri-methyl benzophenone, isopropyl thioxanthone, 2- chlorothiaxanthenone, 1-, 2,4- bis-
At least one of ethyl thioxanthone, 2,4,6- trimethylbenzoy-dipheny phosphine oxide.
As a further improvement of the present invention, the display uses following methods with ultraviolet light mixing cured adhesive
Solidified: first being solidified under ultraviolet light, be then heating and curing.
It adopts this technical solution, is prepared based on polyurethane grafted modified sulfur-bearing epoxy monoacrylate, first pass through purple
Outer Light lnduced Free Radicals solidify, and acrylic double bond energy Quick cross-linking solidification in adhesive system is formed to the preliminary glutinous of substrate
It connects, then under heating conditions, the epoxy group in system realizes heat cure, bonding action is further increased,
As a further improvement of the present invention, the polyurethane grafted modified sulfur-bearing epoxy third that the grafting rate is 50% or more
Olefin(e) acid monoesters is prepared using following methods step:
Step S1: synthesis sulfur-bearing epoxy monoacrylate segment;
Step S2: synthesis of polyurethane acrylate segment;
Step S3: the sulfur-bearing epoxy monoacrylate segment and step S2 that step S1 synthesis is added into reaction vessel close
At urethane acrylate segment, and dibutyl tin dilaurate is added, wherein account for the dibutyl of gross mass 0.1~0.5%
The additional amount of tin dilaurate tin, sulfur-bearing epoxy monoacrylate segment and urethane acrylate segment meets sulfur-bearing propylene oxide
Acid esters and-NCO group molar ratio are 1:0.5~1, and mass percent shared by dibutyl tin dilaurate is 0.1~0.3%;
3~6h is reacted at 60~100 DEG C, obtains urethane acrylate modified sulfur-bearing epoxy third of the grafting rate control 50% or more
Olefin(e) acid monoesters resin.
It adopts this technical solution, based on the high refractive power resin of the sulfur-bearing of novel belt acrylic double bond and epoxy group,
The ultraviolet light mixing cured adhesive of high refractive power is prepared, it is solid which can be used for the gluing in display between each optical material
It is fixed.
As a further improvement of the present invention, step S1 synthesize sulfur-bearing epoxy monoacrylate segment the following steps are included:
Epoxychloropropane is added in the reaction vessel, is heated with stirring to 50~90 DEG C, two mercaptan are then added, the additional amount of two mercaptan is full
The molar ratio of two mercaptan of foot and epoxychloropropane is 1:5~10;Then the mass concentration that same volume is added is 15%-20% hydrogen-oxygen
Change sodium solution, be stirred to react 0.5~2h, after cooling, the ether of 2~5 times of volumes and the distilled water of 2~5 times of volumes is added, separates
Organic layer is washed to neutrality, is dried, filtered with anhydrous magnesium sulfate, and decompression removal solvent obtains sulfur-bearing epoxy;Contain resulting
Sulphur epoxy is added in reaction vessel, is heated with stirring to 90~130 DEG C, is then added and accounts for the catalysis that mass fraction is 0.1~1.0%
Agent N, N- dimethyl benzylamine and 0.1~1.0% polymerization inhibitor p-hydroxyanisole;Acrylic or methacrylic acid is added, institute
It is 2:1 that the additional amount for stating acrylic or methacrylic acid, which meets epoxy group and the molar ratio of acrylic acid,;The reaction was continued 2~6h,
When by acid value≤3mgKOH/g of alkalimetric titration to system, sulfur-bearing epoxy monoacrylate segment is obtained.
As a further improvement of the present invention, two mercaptan is 2,4- dimercapto pyrimidine, 4,4'- dimercapto diphenyl sulfide
Pungent two mercaptan of ether, 1,6- ethanthiol, 2,5- dimercaptothiodiazole, 1,8-, 1,2- dithioglycol, 1,3- dimercaptopropane, 1,
At least one of two mercaptan of 9- nonyl, 1,7- heptan, two mercaptan, pungent two mercaptan of 3,6- dioxy -1,8-.
As a further improvement of the present invention, step S2 synthesis of polyurethane acrylate segment is the following steps are included: anti-
It answers and diisocyanate is added in container, be heated with stirring to 50~90 DEG C, two mercaptan or dihydric alcohol are then added dropwise to diisocyanate
In ester, dibutyl tin dilaurate is added in two mercaptan or dihydric alcohol, wherein the additional amount of two mercaptan or dihydric alcohol is full
The molar ratio of sufficient diisocyanate and two mercaptan or dihydric alcohol is 2:1, and mass percent shared by dibutyl tin dilaurate is
0.1~1.0%;After reacting 2~6h, the hydroxy-ethyl acrylate for being added with p-hydroxyanisole is added into reaction system, wherein
It is 1~1.1:2 that the additional amount of hydroxy-ethyl acrylate, which meets hydroxy-ethyl acrylate and the molar ratio of 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, the reaction was continued 2~5h,
Have to one end-NCO group and the other end for acrylic double bond urethane acrylate segment.
As a further improvement of the present invention, the diisocyanate is toluene di-isocyanate(TDI) (TDI), diphenyl methane
Diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride
At least one of diisocyanate (HMDI), paraphenylene diisocyanate (PPDI);
As a further improvement of the present invention, two mercaptan is 2,4- dimercapto pyrimidine, 4,4'- dimercapto diphenyl sulfide
Pungent two mercaptan of ether, 1,6- ethanthiol, 2,5- dimercaptothiodiazole, 1,8-, 1,2- dithioglycol, 1,3- dimercaptopropane, 1,
At least one of two mercaptan of 9- nonyl, 1,7- heptan, two mercaptan, pungent two mercaptan of 3,6- dioxy -1,8-.
As a further improvement of the present invention, the dihydric alcohol is polyether Glycols, polyester diol, propylene glycol, new penta
At least one of glycol, 1,4-butanediol, 1,6- hexylene glycol.
The invention also discloses a kind of display as described above preparation methods of ultraviolet light mixing cured adhesive, first
Polyurethane grafted modified sulfur-bearing epoxy monoacrylate is uniformly mixed with reactive diluent, then be added photoinitiator and
Thermal curing agents stir at low speed, and vacuum vibration deaeration is to get ultraviolet light mixing cured adhesive.
Technical side's scheme of the invention combines the characteristics of ultraviolet light solidifies, the ultraviolet light solidified body of single acrylate
System has many advantages, such as that fast curing rate, initiator type and resin types are all more, but there is also cubical contractions after solidification
Greatly, adhesive force and the disadvantages of limited bonding action.In such a way that ultraviolet light solidification is in conjunction with heat cure, two kinds can be effectively played
The advantages of curing mode, while the shrinking percentage of curing system can be reduced, improve bonding action.
The invention has the benefit that
Using technical solution of the present invention, acrylate structure will be introduced with the sulfur-containing group of high refractive property
In, while synthetic technology is utilized, make in resin structure while there is photo curable acrylic double bond and heat-setting ring
Oxygen groups.After the resin and reactive diluent etc. are prepared, after ultraviolet light, double bond rapid curing in resin, to glass
Equal substrates provide preliminary cementability, then make the epoxy group curing reaction in system under the action of heat, due to epoxy
The presence of group reduces the double bond density in system, can also reduce the cubical contraction of solidification process, mixed in ultraviolet-heat
It closes under solidification, adhesive, which has, solidifies higher bonding action than single ultraviolet light, and the bonding coat after solidifying has
The characteristic of high refractive power, refraction index >=1.50;The gluing for being able to satisfy optical component in display is fixed, and also can solve existing glue
The defects such as glutinous agent refraction index is low.The gluing that can be applied to optical component etc. in LCD/LED display is fixed.
Specific embodiment
Preferably embodiment of the invention is described in further detail below.
Embodiment 1
A kind of ultraviolet light mixing cured adhesive of display comprising component and its parts by weight are as follows:
The polyurethane grafted modified sulfur-bearing epoxy monoacrylate 72 that grafting rate is 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
The grafting rate be 70% polyurethane grafted modified sulfur-bearing epoxy acrylate the preparation method comprises the following steps:
The epoxychloropropane of 3mol is added in 1000mL three-necked flask, is heated with stirring to 50 DEG C, adds for the first step
1, the 6- ethanthiol of 0.5mol adds the 20%NaOH solution of about 300mL, is stirred to react 2h, is cooled to room temperature, and is added 3
Times ether of volume and the distilled water of 4 times of volumes, separate organic layer, are washed to neutrality, dried, filtered with anhydrous magnesium sulfate, subtracted
Pressure removal solvent, obtains sulfur-bearing epoxy;The sulfur-bearing epoxy for weighing the above-mentioned synthesis of 0.3mol is added in 500mL three-necked flask, stirring
Be heated to 110 DEG C, then be added account for mass fraction be 0.8% catalyst n, N- dimethyl benzylamine and 0.6% polymerization inhibitor to hydroxyl
Base methyl phenyl ethers anisole;The acrylic acid of 0.3mol is added, 1. the reaction was continued 4h obtains sulfur-bearing epoxy monoacrylate segment;
The toluene di-isocyanate(TDI) (TDI) of 1.0mol is added in the three-necked flask of 1000mL, is heated to 50 for second step
DEG C, 1,9- nonyl, two mercaptan that dibutyl tin dilaurate is added to 0.5mol by the 1.0% of gross mass is added dropwise to toluene diisocyanate
In acid esters (TDI) solution, 0.6% para hydroxybenzene is added in the reaction was continued 6h after dripping off in the hydroxy-ethyl acrylate of 0.5mol
Above-mentioned reaction system is added in methyl ether, be warming up to 90 DEG C of reaction 2.5h to get to one end band NCO group and the other end be acrylic acid
The sulfur-containing polyurethane acrylate segment of ester double bond is 2.;
1. third step, the sulfur-bearing epoxy monoacrylate that 0.2mol is added in the three-necked flask of 500mL, are added
2. the sulfur-containing polyurethane acrylate of 0.14mol, is added the dibutyl tin dilaurate for accounting for gross mass 0.1%, is heated at 80 DEG C
3h is reacted to get the modified sulfur-bearing epoxy monoacrylate resin of urethane acrylate for being 70% to grafting rate.
The display is with the preparation method of ultraviolet light mixing cured adhesive: being first 70% by the grafting rate 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 photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone and heat cure is then added
The aliphatic modified amine of agent stirs at low speed, and vacuum vibration deaeration is to get the ultraviolet light mixing cured adhesive of high refractive power.
Obtained adhesive is coated on glass substrate, its performance is tested after ultraviolet-heat is mixing cured, is detected
The adhesive adhesive strength of the present embodiment is 2.3MPa(compression shear strength), there are good alcohol resistance and water resistance, refraction index is
1.5213。
Embodiment 2
A kind of ultraviolet light mixing cured adhesive of display comprising component and its parts by weight are as follows:
Grafting rate is 100% polyurethane grafted modified sulfur-bearing epoxy monoacrylate 80
Hydroxy-ethyl acrylate 5
Dipropylene glycol diacrylate 6
Trimethylolpropane trimethacrylate 3
1- hydroxycyclohexyl phenyl ketone 3
Dicyandiamide 3
The grafting rate be 100% polyurethane grafted modified sulfur-bearing epoxy acrylate the preparation method comprises the following steps:
The epoxychloropropane of 3mol is added in 1000mL three-necked flask, is heated with stirring to 65 DEG C, adds for the first step
2, the 5- dimercaptothiodiazole of 0.6mol adds the 18%NaOH solution of about 300mL, is stirred to react 1h, is cooled to room temperature, add
Enter the ether of 3 times of volumes and the distilled water of 3 times of volumes, separate organic layer, be washed to neutrality, dried, filtered with anhydrous magnesium sulfate,
Decompression removal solvent, obtains sulfur-bearing epoxy;The sulfur-bearing epoxy for weighing the above-mentioned synthesis of 0.3mol is added in 500mL three-necked flask, stirs
Mix and be heated to 115 DEG C, then be added account for mass fraction be 0.7% catalyst n, N- dimethyl benzylamine and 0.9% polymerization inhibitor pair
Hydroxyanisol;The acrylic acid of 0.3mol is added, 1. the reaction was continued 3.5h obtains sulfur-bearing epoxy monoacrylate segment;
The isophorone diisocyanate (IPDI) of 2.0mol, heating is added in second step in the three-necked flask of 1000mL
To 75 DEG C, 4, the 4'- dimercapto diphenyl sulfide that dibutyl tin dilaurate is added to 1mol by the 0.5% of gross mass is added dropwise to
In isophorone diisocyanate (IPDI) solution, the reaction was continued 4h after dripping off is added in the hydroxy-ethyl acrylate of 1mol
Above-mentioned reaction system is added in 0.4% p-hydroxyanisole, is warming up to 85 DEG C of reaction 3h to get to one end band NCO group and separately
One end be acrylic double bond sulfur-containing polyurethane acrylate segment 2.;
1., 0.2mol is added in third step, the sulfur-bearing epoxy monoacrylate that 0.2mol is added in the three-necked flask of 500mL
Sulfur-containing polyurethane acrylate 2., be added and account for the dibutyl tin dilaurate of gross mass 0.3%, be heated to reacting at 75 DEG C
4.5h is to get the modified sulfur-bearing epoxy monoacrylate resin of urethane acrylate for being 100% to grafting rate.
The preparation method is the same as that of Example 1 with ultraviolet light mixing cured adhesive for the display.
Obtained adhesive is coated on glass substrate, its performance is tested after ultraviolet-heat is mixing cured, detects this hair
Bright adhesive bonding action is 2.5MPa(compression shear strength), there are good alcohol resistance and water resistance, refraction index 1.5932.
Embodiment 3
A kind of ultraviolet light mixing cured adhesive of display comprising component and its parts by weight are as follows:
The polyurethane grafted modified sulfur-bearing epoxy monoacrylate 60 that grafting rate is 50%
Hydroxypropyl acrylate 5
Phthalic acid diethylene glycol diacrylate 8
Ethoxylated neopentylglycol diacrylate 10
Ethoxylated trimethylolpropane triacrylate 10
Isopropyl thioxanthone 3
Diethylaminopropylamine 4
The grafting rate be 50% polyurethane grafted modified sulfur-bearing epoxy acrylate the preparation method comprises the following steps:
The epoxychloropropane of 3mol is added in 1000mL three-necked flask, is heated with stirring to 60 DEG C, adds for the first step
0.6mol, 4,4'- dimercapto diphenyl sulfide, add the 15%NaOH solution of about 300mL, are stirred to react 1h, are cooled to room
Temperature is added the ether of 4 times of volumes and the distilled water of 5 times of volumes, separates organic layer, be washed to neutrality, dry with anhydrous magnesium sulfate,
Filtering, decompression removal solvent, obtains sulfur-bearing epoxy;500mL three-necked flask is added in the sulfur-bearing epoxy for weighing the above-mentioned synthesis of 0.4mol
In, be heated with stirring to 130 DEG C, then be added account for mass fraction be 0.6% catalyst n, N- dimethyl benzylamine and 1.0% resistance
Poly- agent p-hydroxyanisole;The acrylic acid of 0.4mol is added, the reaction was continued 3h obtains sulfur-bearing epoxy monoacrylate segment
①;
The methyl diphenylene diisocyanate (MDI) of 2.0mol, heating is added in second step in the three-necked flask of 1000mL
To 60 DEG C, the polyether Glycols that dibutyl tin dilaurate is added to 1mol by the 0.8% of gross mass are added dropwise to diphenyl methane
In diisocyanate (MDI) solution, 0.3% pair is added in the reaction was continued 4.5h after dripping off in the hydroxy-ethyl acrylate of 1mol
Above-mentioned reaction system is added in hydroxyanisol, be warming up to 95 DEG C of reaction 2h to get to one end band NCO group and the other end be third
The urethane acrylate segment of olefin(e) acid ester double bond is 2.;
1. third step, the sulfur-bearing epoxy monoacrylate that 0.3mol is added in the three-necked flask of 500mL, are added
.0.15mol 2. sulfur-containing polyurethane acrylate, is added the dibutyl tin dilaurate for accounting for gross mass 0.2%, is heated to 65 DEG C
Lower reaction 5h is to get the modified sulfur-bearing epoxy monoacrylate resin of urethane acrylate for being 50% to grafting rate.
The preparation method is the same as that of Example 1 with ultraviolet light mixing cured adhesive for the display.
Obtained adhesive is coated on glass substrate, ultraviolet light solidification is first passed through, after being then heating and curing, tests it
Performance, detecting adhesive bonding action of the invention is 1.9MPa(compression shear strength), there are good alcohol resistance and water resistance, refractive power
Index is 1.5051.
Comparative example 1
If grafting rate is lower during polyurethane grafted modified sulfur-bearing epoxy acrylate, adhesive gluing also will affect
Intensity and refraction index.
The adhesive of comparison comprising component and its parts by weight are as follows:
Polyurethane grafted modified sulfur-bearing epoxy monoacrylate (50% or less graft modification rate) 55
Hydroxy-ethyl acrylate 10
Dipropylene glycol diacrylate 8
Ethoxylated neopentylglycol diacrylate 10
Ethoxylated trimethylolpropane triacrylate 10
Isopropyl thioxanthone 3
Diethylaminopropylamine 4
The polyurethane grafted modified sulfur-bearing epoxy acrylate the preparation method comprises the following steps:
The epoxychloropropane of 3mol is added in 1000mL three-necked flask, is heated with stirring to 60 DEG C, adds for the first step
0.6mol, 4,4'- dimercapto diphenyl sulfide, add the 15%NaOH solution of about 300mL, are stirred to react 1h, are cooled to room
Temperature is added the ether of 4 times of volumes and the distilled water of 5 times of volumes, separates organic layer, be washed to neutrality, dry with anhydrous magnesium sulfate,
Filtering, decompression removal solvent, obtains sulfur-bearing epoxy;500mL three-necked flask is added in the sulfur-bearing epoxy for weighing the above-mentioned synthesis of 0.4mol
In, be heated with stirring to 130 DEG C, then be added account for mass fraction be 0.6% catalyst n, N- dimethyl benzylamine and 1.0% resistance
Poly- agent p-hydroxyanisole;The acrylic acid of 0.4mol is added, the reaction was continued 3h obtains sulfur-bearing epoxy monoacrylate segment
①;
The methyl diphenylene diisocyanate (MDI) of 2.0mol, heating is added in second step in the three-necked flask of 1000mL
To 60 DEG C, the polyether Glycols that dibutyl tin dilaurate is added to 1mol by the 0.8% of gross mass are added dropwise to diphenyl methane
In diisocyanate (MDI) solution, 0.3% pair is added in the reaction was continued 4.5h after dripping off in the hydroxy-ethyl acrylate of 1mol
Above-mentioned reaction system is added in hydroxyanisol, be warming up to 95 DEG C of reaction 2h to get to one end band NCO group and the other end be third
The urethane acrylate segment of olefin(e) acid ester double bond is 2.;
1. third step, the sulfur-bearing epoxy monoacrylate that 0.3mol is added in the three-necked flask of 500mL, are added
2. the sulfur-containing polyurethane acrylate of 0.06mol, is added the dibutyl tin dilaurate for accounting for gross mass 0.2%, is heated at 65 DEG C
It reacts 5h and is modified sulfur-bearing epoxy monoacrylate resin, graft modification to get to the urethane acrylate of graft modification rate 20%
Below rate 50%.
The preparation method is the same as that of Example 1 for adhesive.
Obtained adhesive is coated on glass substrate, its performance is tested after ultraviolet-heat is mixing cured, detects this hair
Bright adhesive bonding action is 1.4MPa(compression shear strength), there are good alcohol resistance and water resistance, refraction index 1.4783.
Comparative example 2
Common display is mostly thermohardening type with adhesive at present comprising component and its parts by weight are as follows:
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
Above-mentioned substance is carried out to be mixed to get adhesive, adhesive is coated on glass substrate, 120 DEG C or so solidification 2-
Its performance is tested after 3h, detection adhesive bonding action is 1.47MPa(compression shear strength), refraction index 1.2879.
From the point of view of curing mode and test result, traditional display packaging plastic is mostly single thermohardening type, such as will be in height
Temperature is lower fixed for a long time and is solidified, and influences production efficiency, and its refraction index only has 1.2879.
By the test result to 1 ~ embodiment of embodiment 3 and comparative example 1, comparative example 1 compare come
It sees, adhesive of the invention has the advantage that
(1) due to selecting modified resin and by control grafting rate and formula adjustment, adhesive of the present invention can be ultraviolet
Rapid curing (within 10s) provides preliminary bonding action under light, and such adhesive can tentatively be formed, and not needing fixation can be again
Thermosetting further increases bonding action, and bonding action is higher than common display heat cure adhesive.It is set by control
The grafting rate of rouge, bonding action generally can achieve 1.9MPa or more, left higher than the 1.4MPa of common heat curing type adhesive
It is right.
(2) present invention is by control the methods of grafting rate and group containing S, so that the index of refraction after adhesive solidifies reaches
1.5 or more, it to be significantly higher than the index of refraction of common heat curing type adhesive, performance change is obvious, can be applied to diopter
Demanding display gluing field.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (9)
1. a kind of application of ultraviolet light mixing cured adhesive in the glass baseplate bonding of display, it is characterised in that: described
The component and its parts by weight that ultraviolet light mixing cured adhesive includes are as follows: the polyurethane grafted modification that grafting rate is 50% or more
Sulfur-bearing epoxy monoacrylate, 40~90 parts;Reactive diluent, 10~45 parts;Photoinitiator, 1~5 part;Thermal curing agents 1~
10 parts;The reactive diluent is monofunctional diluent, difunctional diluent, one or more of in trifunctional diluent
Mixture;Wherein, the monofunctional diluent is glycidyl acrylate, butyl acrylate, methyl acrylate, propylene
At least one of sour hydroxyl ethyl ester, hydroxypropyl acrylate, N- ethylene pyrrole alkanone;The difunctional diluent is phthalic acid
Diethylene glycol diacrylate, phthalic acid tripropylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol two
Acrylate, neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, 1,6 hexanediol diacrylate,
1,4 butanediol diacrylate, ethoxylated bisphenol a diacrylate, diethylene glycol diacrylate, triethylene glycol dipropyl
At least one of olefin(e) acid ester;The trifunctional diluent is trimethylolpropane trimethacrylate, three hydroxyl first of ethoxylation
At least one of base propane triacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate.
2. application of the ultraviolet light mixing cured adhesive according to claim 1 in the glass baseplate bonding of display,
It is characterized by: component and its parts by weight that the ultraviolet light mixing cured adhesive includes are as follows: grafting rate is 50% or more
Polyurethane grafted modified sulfur-bearing epoxy monoacrylate, 60~80 parts;Reactive diluent, 14~33 parts;Photoinitiator, 3~4
Part;3~5 parts of thermal curing agents.
3. application of the ultraviolet light mixing cured adhesive according to claim 1 in the glass baseplate bonding of display,
It is characterized by: the photoinitiator is benzoin and its derivatives, benzil derivatives, Dialkoxy acetophenones, α-hydroxyl alkane
At least one of base benzophenone, α-amine alkyl phenones, acylphosphine oxide, benzophenone or heterocycle arone compounds;The heat
Curing agent is ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, aliphatic modified amine, aromatic amine, O-phthalic
The mixture of one or more of acid anhydrides, dicyandiamide.
4. the answering in the glass baseplate bonding of display according to claim 3 with ultraviolet light mixing cured adhesive
With, it is characterised in that: the photoinitiator be benzoin methyl ether, benzoin ethyl ether, styrax n-butyl ether, diphenylthanedione,
Dialkoxy acetophenones, chloroacetophenone, benzophenone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl benzene
Base ketone, 4- methyl benzophenone, 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 2,4,6- trimethyl hexichol first
The chloro- 4- propoxyl group thioxanthone of ketone, isopropyl thioxanthone, 2- chlorothiaxanthenone, 1-, 2,4- diethyl thioxanthone, 2,4,
At least one of 6- trimethylbenzoy-dipheny phosphine oxide.
5. the answering in the glass baseplate bonding of display according to claim 1 with ultraviolet light mixing cured adhesive
With, it is characterised in that: the ultraviolet light mixing cured adhesive is solidified using following methods: first being consolidated under ultraviolet light
Change, is then heating and curing.
6. viscous in the glass baseplate of display with ultraviolet light mixing cured adhesive described in any one according to claim 1 ~ 5
Application in knot, it is characterised in that: the polyurethane grafted modified sulfur-bearing epoxy monoacrylate that the grafting rate is 50% or more is adopted
Step is prepared using the following method:
Step S1: synthesis sulfur-bearing epoxy monoacrylate segment;
Step S2: synthesis of polyurethane acrylate segment;
Step S3: what the sulfur-bearing epoxy monoacrylate segment and step S2 that step S1 synthesis is added into reaction vessel synthesized
Urethane acrylate segment, and dibutyl tin dilaurate is added, wherein account for the dibutyl tin of gross mass 0.1~0.5%
The additional amount of cinnamic acid tin, sulfur-bearing epoxy monoacrylate segment and urethane acrylate segment meets sulfur-bearing epoxy acrylate
It is 1:0.5~1 with-NCO group molar ratio, mass percent shared by dibutyl tin dilaurate is 0.1~0.3%;60
3~6h is reacted at~100 DEG C, obtains urethane acrylate modified sulfur-bearing epoxy acrylic of the grafting rate control 50% or more
Monoesters resin.
7. the answering in the glass baseplate bonding of display according to claim 6 with ultraviolet light mixing cured adhesive
With, it is characterised in that: step S1 synthesizes sulfur-bearing epoxy monoacrylate segment the following steps are included: ring is added in the reaction vessel
Oxygen chloropropane, is heated with stirring to 50~90 DEG C, and two mercaptan are then added, and the additional amount of two mercaptan meets two mercaptan and epoxy chloropropionate
The molar ratio of alkane is 1:5~10;Then the mass concentration that same volume is added is 15%-20% sodium hydroxide solution, is stirred to react
0.5~2h after cooling, be added the ether of 2~5 times of volumes and the distilled water of 2~5 times of volumes, separate organic layer, is washed to
Property, it is dried, filtered with anhydrous magnesium sulfate, decompression removal solvent obtains sulfur-bearing epoxy;Reaction is added in resulting sulfur-bearing epoxy to hold
In device, 90~130 DEG C are heated with stirring to, is then added and accounts for the catalyst n that mass fraction is 0.1~1.0%, N- dimethyl benzylamine
With 0.1~1.0% polymerization inhibitor p-hydroxyanisole;Add acrylic or methacrylic acid, the acrylic or methacrylic
It is 2:1 that the additional amount of acid, which meets epoxy group and the molar ratio of acrylic acid,;The reaction was continued 2~6h, passes through alkalimetric titration to system
When acid value≤3mgKOH/g, sulfur-bearing epoxy monoacrylate segment is obtained;
Two mercaptan is 2,4- dimercapto pyrimidine, 4,4'- dimercapto diphenyl sulfide, 1,6- ethanthiol, 2,5- dimercapto
Pungent two mercaptan of thiadiazoles, 1,8-, 1,2- dithioglycol, 1,3- dimercaptopropane, 1,9- nonyl, two mercaptan, 1,7- heptan, two mercaptan, 3,6-
At least one of pungent two mercaptan of dioxy -1,8-.
8. the answering in the glass baseplate bonding of display according to claim 6 with ultraviolet light mixing cured adhesive
With, it is characterised in that: step S2 synthesis of polyurethane acrylate segment the following steps are included: be added two isocyanides in the reaction vessel
Acid esters is heated with stirring to 50~90 DEG C, and then two mercaptan or dihydric alcohol are added dropwise in diisocyanate, two mercaptan or two
Dibutyl tin dilaurate is added in first alcohol, wherein the additional amount of two mercaptan or dihydric alcohol meets diisocyanate and two sulphur
The molar ratio of alcohol or dihydric alcohol is 2:1, and mass percent shared by dibutyl tin dilaurate is 0.1~1.0%;React 2~6h
Afterwards, the hydroxy-ethyl acrylate for being added with p-hydroxyanisole is added into reaction system, wherein the additional amount of hydroxy-ethyl acrylate
The molar ratio for meeting hydroxy-ethyl acrylate and diisocyanate is 1~1.1:2, quality hundred shared by the p-hydroxyanisole
Divide than being 0.1~1.0%;Reaction system is heated to 60~100 DEG C, the reaction was continued 2~5h, obtain to one end have-NCO group and
The other end is the urethane acrylate segment of acrylic double bond;
The diisocyanate is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), hexa-methylene two
It is isocyanates (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate (HMDI), different to benzene two
At least one of cyanate (PPDI);
Two mercaptan is 2,4- dimercapto pyrimidine, 4,4'- dimercapto diphenyl sulfide, 1,6- ethanthiol, 2,5- dimercapto
Pungent two mercaptan of thiadiazoles, 1,8-, 1,2- dithioglycol, 1,3- dimercaptopropane, 1,9- nonyl, two mercaptan, 1,7- heptan, two mercaptan, 3,6-
At least one of pungent two mercaptan of dioxy -1,8-;
The dihydric alcohol is polyether Glycols, polyester diol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6- hexylene glycol
At least one of.
9. application of the ultraviolet light mixing cured adhesive according to claim 1 in the glass baseplate bonding of display,
It is characterized by: the preparation method of the ultraviolet light mixing cured adhesive includes: first by polyurethane grafted modified sulfur-bearing epoxy
Acrylic monoester is uniformly mixed with reactive diluent, and photoinitiator then is added and thermal curing agents stir at low speed, very
Sky vibration deaeration is to get ultraviolet light mixing cured adhesive.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610265474.8A CN105754545B (en) | 2016-04-26 | 2016-04-26 | A kind of display ultraviolet light mixing cured adhesive and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610265474.8A CN105754545B (en) | 2016-04-26 | 2016-04-26 | A kind of display ultraviolet light mixing cured adhesive and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105754545A CN105754545A (en) | 2016-07-13 |
CN105754545B true CN105754545B (en) | 2019-04-09 |
Family
ID=56325849
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610265474.8A Active CN105754545B (en) | 2016-04-26 | 2016-04-26 | A kind of display ultraviolet light mixing cured adhesive and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105754545B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109971385A (en) * | 2017-12-27 | 2019-07-05 | 东莞新科技术研究开发有限公司 | Ultraviolet cured adhesive film |
CN110016144B (en) * | 2019-04-03 | 2021-08-03 | 深圳职业技术学院 | Water-soluble polyfunctional resin and preparation method thereof |
CN110016295B (en) * | 2019-04-09 | 2021-04-16 | 浙江国能科技有限公司 | Optical adhesive for repairing cracks of touch screen and application thereof |
CN111534269B (en) * | 2020-05-07 | 2022-04-12 | 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 |
CN114276539B (en) * | 2021-12-30 | 2023-04-25 | 北京林业大学 | Thiol-modified PAE resin cross-linking agent, modified protein adhesive and preparation method thereof |
CN115595001B (en) * | 2022-09-09 | 2024-01-09 | 杭州光粒科技有限公司 | Photosensitive polymer composition, preparation method thereof and holographic diffraction grating element |
CN115820015B (en) * | 2022-12-08 | 2023-08-01 | 西安思摩威新材料有限公司 | UV curable composition in air, OLED light extraction film and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102993410A (en) * | 2012-11-30 | 2013-03-27 | 深圳职业技术学院 | Method for preparing sulfur-containing high-refractive-index resin |
CN103289049A (en) * | 2013-06-07 | 2013-09-11 | 深圳职业技术学院 | Preparation method for dual-curing group-containing high-refraction resin |
CN103709365A (en) * | 2013-12-13 | 2014-04-09 | 深圳职业技术学院 | High refractive resin containing silicon and preparation method of resin |
-
2016
- 2016-04-26 CN CN201610265474.8A patent/CN105754545B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102993410A (en) * | 2012-11-30 | 2013-03-27 | 深圳职业技术学院 | Method for preparing sulfur-containing high-refractive-index resin |
CN103289049A (en) * | 2013-06-07 | 2013-09-11 | 深圳职业技术学院 | Preparation method for dual-curing group-containing high-refraction resin |
CN103709365A (en) * | 2013-12-13 | 2014-04-09 | 深圳职业技术学院 | High refractive resin containing silicon and preparation method of resin |
Also Published As
Publication number | Publication date |
---|---|
CN105754545A (en) | 2016-07-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105754545B (en) | A kind of display ultraviolet light mixing cured adhesive and preparation method thereof | |
CN105713550B (en) | A kind of ultraviolet light solidification optical cement and preparation method thereof for Glass optical device | |
CN102234268B (en) | Method for preparing ultraviolet (UV)-curable polyisocyanate modified superbranched epoxy acrylate | |
KR101330443B1 (en) | Transfer sheet and process for producing same | |
CN105121513B (en) | Ene-thiol-type curable composition and cured product thereof | |
CN108383974A (en) | A kind of ultraviolet light solidification high-strength polyurethane acrylate and preparation method thereof | |
CN113355017B (en) | Low-refractive-index optical fiber coating resin with high glass transition temperature | |
CN101805422B (en) | Energy ray-curable resin composition and cured product for optical lens sheet | |
CN103509516B (en) | Ultraviolet-curing adhesive resin combination and adhesive | |
WO2007086461A1 (en) | Curable composition containing thiol compound | |
CN104321306A (en) | Production method for polythiol compound, polymerizable composition for optical material and use therefor | |
WO2008035643A1 (en) | Resin composition for optical material and optical material using the same | |
CN101675082A (en) | Resin composition for optical member and optical member obtained from the same | |
CN109762509B (en) | UV (ultraviolet) viscosity reducing adhesive and application thereof | |
CN101885809A (en) | Energy ray curable resin composition and cured article thereof and optical lens | |
CN108102558A (en) | A kind of high intensity is wet, light dual cure polyurethane binder and preparation method thereof and application method | |
CN111777982A (en) | Yellowing-resistant solvent-free polyurethane composite adhesive and preparation method thereof | |
CN110483730A (en) | A kind of polyurethane acrylic ester oligomer and the preparation method and application thereof method | |
CN109294460B (en) | Yellowing-resistant UV (ultraviolet) curing liquid optical transparent adhesive and preparation method thereof | |
CN109651961A (en) | A kind of acrylate pressure sensitive adhesive, photo-thermal dual curable glue film and preparation method thereof | |
JP2007277309A (en) | Crystalline resin composition and its manufacturing method | |
CN109535366A (en) | A kind of secondary amino silanes modified polyether polymer and preparation method thereof | |
CN111139020A (en) | Thermosetting and UV curing composite adhesive and preparation method thereof | |
KR20010037679A (en) | Resin composition for manufacturing optic fiber ribbon and a method for manufacturing optic fiber ribbon using the same | |
FI86882B (en) | FOERFARANDE FROSTAELLNING AV BELAEGGNINGAR GENOM TVAERBINDNING MED STRAOLNING. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |