CN111286297B - High-strength ultraviolet/moisture dual-curing adhesive and preparation method and use method thereof - Google Patents
High-strength ultraviolet/moisture dual-curing adhesive and preparation method and use method thereof Download PDFInfo
- Publication number
- CN111286297B CN111286297B CN202010130998.2A CN202010130998A CN111286297B CN 111286297 B CN111286297 B CN 111286297B CN 202010130998 A CN202010130998 A CN 202010130998A CN 111286297 B CN111286297 B CN 111286297B
- Authority
- CN
- China
- Prior art keywords
- parts
- acrylate
- strength
- curing adhesive
- moisture dual
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to the technical field of adhesives, and discloses a high-strength ultraviolet/moisture dual-curing adhesive which is prepared from the following raw materials in parts by weight: 60-75 parts of polyurethane prepolymer, 10-20 parts of reactive diluent, 1-5 parts of photoinitiator, 10-20 parts of polyurethane acrylate, 0.1-0.5 part of filler, 1-2 parts of silane coupling agent and 0.3-0.6 part of catalyst; the polyurethane acrylate is initiated by the free radical initiator, so that the positioning time is reduced, the initial strength is improved, the production efficiency is improved, and the polyurethane acrylate is suitable for the rapid assembly of electronic components on a production line; and provides a preparation method and a use method of the high-strength ultraviolet/moisture dual-curing adhesive.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-strength ultraviolet/moisture dual-curing adhesive and a preparation method and a use method thereof.
Background
The Ultraviolet (UV) curing technology is a high-efficiency, energy-saving and environment-friendly high-new curing technology, has the advantages of fast curing, low energy consumption, high efficiency, no pollution and the like, and has wide application in the aspect of adhesives, but has the limitation that deep layers and object shadow areas are difficult to cure and the like, so that the application range of the UV adhesives is influenced. Moisture-curing reactive Polyurethane (PU) hot melt adhesives are considered a new generation of hot melt adhesives that provide superior performance. The hot melt adhesive with 100 percent of solid content is prepared by taking a moisture curing end isocyanate group polyurethane prepolymer with relatively low average molecular weight as a matrix, and adding thermoplastic resin and tackifying resin which do not react with isocyanate groups, an antioxidant, a catalyst, a filler and the like. The adhesive has excellent initial strength, and also has a cross-linkable curing function, so that the adhesive strength, heat resistance, chemical resistance and durability of a final product are effectively improved, and the automatic, mechanical and high-speed batch production is facilitated; in addition, the solid content of the organic solvent-free paint is 100%, so the paint has good environmental protection property. But the curing process is slow, the initial adhesion is low, and the initial curing time is long.
There have been studies to try to solve the above problems by combining adhesives having uv curing and moisture curing properties. For example, chinese invention patent CN105086916A discloses a high light transmittance UV-moisture dual-curing adhesive, which comprises a polyurethane prepolymer, a reactive diluent, a photoinitiator and other auxiliaries. Wherein the polyurethane prepolymer is synthesized by aliphatic diisocyanate, dihydric alcohol or polyalcohol and epoxy acrylate monoester containing hydroxyl; the photoinitiator is a mixture of a free radical photoinitiator and a cationic photoinitiator, the cationic photoinitiator is an arylferrocenium salt with carbonyl on aromatic hydrocarbon, the curing speed is high, but the production process is complex, the time consumption is long, and the conditions are harsh.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the high-strength ultraviolet/moisture dual-curing adhesive which is initiated by a free radical initiator, reduces the positioning time, improves the initial strength, improves the production efficiency, and is suitable for the assembly line to quickly assemble electronic elements; and provides a preparation method and a use method of the high-strength ultraviolet/moisture dual-curing adhesive.
In order to achieve the first object, the invention provides the following technical scheme:
the high-strength ultraviolet/moisture dual-curing adhesive is prepared from the following raw materials in parts by weight:
the polyurethane prepolymer is prepared by reacting one or a mixture of more of polyether diol and polyester diol with isocyanate, wherein the molar ratio of hydroxyl to isocyanate is 1: 1.0-1.2.
The ultraviolet/moisture curing polyurethane hot melt adhesive disclosed by the invention is initiated by a free radical initiator by using polyurethane acrylate, has higher reaction activity, thereby reducing the positioning time, improving the initial strength and improving the production efficiency, and is suitable for the rapid assembly of electronic elements on a production line.
In the present invention, further, the isocyanate is an aromatic diisocyanate,
the aromatic diisocyanate is one or more of toluene diisocyanate and diphenyl methyl diisocyanate, and the diphenyl diisocyanate refers to one or more of 4, 4 ' -diphenyl methyl diisocyanate, 2, 4 ' -diphenyl methyl diisocyanate and 2, 2 ' -diphenyl methyl diisocyanate and diphenyl methyl diisocyanate modified by carbodiimide;
preferably 4, 4' -diphenylmethyl diisocyanate.
In the present invention, further, the polyether glycol includes but is not limited to one or more of polyoxyethylene glycol with an average molecular weight of 2000-4000 or a mixture thereof with one or more of polypropylene glycol with an average molecular weight of 2000-6000;
preferably polyoxyethylene glycol having an average molecular weight of 2000-4000.
In the invention, the polyester dihydric alcohol further comprises one or a mixture of polyester dihydric alcohol which is formed by polycondensation of adipic acid and one or two of glycol such as ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol and the like and has an average molecular weight of 1000-3000;
preference is given to 1, 4-butanediol polyadipates having an average molecular weight of 2000.
In the present invention, further, the reactive diluent is a monofunctional (meth) acrylate monomer including, but not limited to, butylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, acryloylmorpholine, N-vinylcaprolactam, nonylphenoxypolyethylene glycol (meth) acrylate, N-vinylcaprolactam, N-vinylbenzylmethacrylate, N-vinylbenzylpyrrolidone, N-vinylbenzylmethacrylate, and N-vinylbenzylmethacrylate, Nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like;
2-phenoxyethyl acrylate, cyclotrimethylolpropane formal acrylate and ethoxyethoxyethyl acrylate are preferred.
In the present invention, further, the photoinitiator is a free radical photoinitiator, including but not limited to 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2, 4, 6-trimethylbenzoyl) -phosphine oxide, 2-benzyl-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, benzil dimethyl ketal dimethoxyphenylacetophenone, alpha-hydroxybenzylphenyl ketone, 1-hydroxy-1-methylethylphenyl ketone, oligo-2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone, benzophenone, methyl o-benzoate, methyl n-butyl-1-one, and mixtures thereof, A mixture of two or more of methyl benzoate, 2-diethoxyacetophenone, 2-di-sec-butoxyacetophenone, p-phenylbenzophenone, 2-isopropylthioxanthone, 2-methylanthrone, 2-ethylanthrone, 2-chloroanthrone, 1, 2-benzanthrone, benzoyl ether, benzoin methyl ether, benzoin isopropyl ether, alpha-phenylbenzoin, thioxanthone, diethylthioxanthone, 1, 5-acetonaphthalene, 1-hydroxycyclohexyl phenyl ketone, ethyl p-dimethylaminobenzoate;
preference is given to ethyl 2, 4, 6-trimethylbenzoylphosphonate.
In the present invention, further, the urethane acrylate is a multifunctional urethane acrylate with good flexibility, including but not limited to, Yangxing chemical 6142H-80, 6143A-80, 6148J-75, 615-.
In the present invention, the filler is further hydrophobic fumed silica, including but not limited to, one of AEROSIL R972, AEROSIL R974, AEROSIL R976S, AEROSIL R104, AEROSIL R10, AEROSIL R202, AEROSIL R80S, wacker HDK H13L, H15, H17, H18, H20, H30, cabot CAB-O-SILTS 720;
preferably cabot CAB-O-SILTS 720;
the silane coupling agent is preferably an aminosilane coupling agent, including but not limited to one or a mixture of more of bis [3- (trimethoxy silicon) propyl ] amine and N-N-butyl-3-aminopropyl trimethoxy silane; preferably 3-aminopropyltriethoxysilane;
the catalyst is triethylene diamine.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of a high-strength ultraviolet/moisture dual-curing adhesive comprises the following steps:
heating and dissolving one or more of polyether diol and polyester diol, and dehydrating; cooling, adding isocyanate and an esterification catalyst, stirring for reaction to obtain a required polyurethane prepolymer, and cooling and storing in a dark place; then mixing and stirring the photoinitiator, the reactive diluent, the polyurethane acrylate, the silane coupling agent and the filler in a dark place, then adding the polyurethane prepolymer, and heating and stirring in a dark place; and finally, adding a catalyst, and reacting to obtain the high-strength/moisture dual-curing adhesive.
And after stirring, filtering the uniformly mixed mixture, and filling the mixture into a moisture-proof package through a closed pipeline for closed storage.
The esterification catalyst is bismuth neodecanoate, and can accelerate the reaction of dihydric alcohol and isocyanate; when the mixture is dissolved and dehydrated, heating to 100 ℃, and dehydrating for 0.5h under the vacuum degree of less than 100 Pa; the reaction conditions for preparing the polyurethane prepolymer are as follows: reacting for 2 hours at the vacuum degree of less than 100Pa and the reaction temperature of 85-90 ℃.
According to the preparation method, the production conditions of the adhesive are relatively loose, and the tensile strength of the produced adhesive is higher than that of the adhesive produced by the prior art.
A use method of the high-strength ultraviolet/moisture dual-curing adhesive comprises the following steps:
coating the adhesive on a base material to be bonded;
(ii) irradiating the coated area with ultraviolet light;
(iii) laminating the substrates to be bonded;
(IV) placing the bonded part obtained in the step (III) at room temperature until the part is completely cured.
More specifically, the method of use comprises the steps of: the adhesive of the present invention can be dispensed by pressing the syringe of an automatic dispenser along a predetermined dispensing path to the surface of a substrate, and then irradiated with 500-1000mJ/cm using a 365nm or 395nm UV-LED lamp such as Nitride NS355L-5RLO2UV curing is generally carried out for a time of about 3s to 10 s; and pressing the other substrate on the adhesive, and controlling the height difference between the two substrates by a laminating machine.
Wherein the substrate may be selected from the group consisting of metal, plastic, ceramic, glass.
According to the invention, an ultraviolet curing technology is combined with a polyurethane hot melt adhesive, so that a crosslinking reaction occurs in the early stage of the dual-curing adhesive system through curing initiated by UV, and then the curing reaction is compensated by moisture curing, and the initiation mechanisms and the curing processes of the two curing reactions are independent and exist simultaneously; better pressure sensitivity and initial adhesion are formed by UV curing in the initial stage, and higher final adhesion is formed by moisture curing of a polyurethane system in the later stage.
Based on the moisture curing characteristic of the adhesive, the primary curing speed is high, additional equipment and process are not needed after primary curing, the attached part can be completely cured after being placed at room temperature for about 24 hours, the production time is effectively shortened, and the process is simpler.
Compared with the prior art, the invention has the beneficial effects that:
the initiator selected in the invention is a free radical initiator, and the reaction activity of the initiator matched with polyurethane acrylate and corresponding isocyanate is higher, so that the positioning time is reduced, the initial strength is improved, the production efficiency is improved, and the method is suitable for the rapid assembly of electronic components on a production line.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the embodiment. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The raw materials used in the invention can be purchased from the market.
Example 1
A high-strength ultraviolet/moisture dual-curing adhesive is prepared by uniformly mixing 3000-average molecular weight polytetrahydrofuran (PTMG3000) and 2000-average molecular weight polypropylene glycol (PPG 2000), heating for dissolving, heating to 100 deg.C, and dehydrating for 0.5 hr under vacuum degree of less than 100 Pa; cooling to 70 ℃, adding 4, 4' -diphenylmethane diisocyanate and new bismuth decanoate, stirring, reacting for 2 hours under the conditions that the vacuum degree is less than 100Pa and the reaction temperature is 70 ℃ to obtain the required polyurethane prepolymer, and cooling and storing in a dark place;
mixing and stirring a photoinitiator, an active diluent, polyurethane acrylate, a silane coupling agent and a filler at 70 ℃ in a dark place, then adding the polyurethane prepolymer, heating to 80 ℃, and stirring for 1h in a dark place under the vacuum degree of less than 100 Pa; finally, adding a catalyst, and continuously reacting for 1h at the vacuum degree of less than 100Pa and the reaction temperature of 70-80 ℃ to obtain the high-strength/moisture dual-curing adhesive;
and after stirring, filtering the uniformly mixed mixture, and filling the mixture into a moisture-proof package through a closed pipeline for closed storage.
In the process, 1 part of ethyl 2, 4, 6-trimethylbenzoylphosphonate, 7.5 parts of 2-phenoxyethyl acrylate, 8 parts of cyclotrimethylolpropane methylal acrylate and 4 parts of ethoxy ethyl acrylate, 5 parts of urethane acrylate (EBECRYL 8413), 1.2 parts of coupling agent (KH-550), 0.8 part of fumed silica, 72 parts of polyurethane prepolymer and 0.5 part of dimorpholinodiethyl ether; wherein the molar ratio of 4, 4' -diphenylmethane diisocyanate, PTMG-3000 and PPG-2000 in the polyurethane prepolymer is 2: 0.8: 0.2; the dosage of the new bismuth decanoate is 0.2 percent of that of the polyether glycol and the 4, 4' -diphenylmethane diisocyanate.
Example 2
A high-strength ultraviolet/moisture dual-curing adhesive is prepared by uniformly mixing 2000 average molecular weight polytetrahydrofuran (PTMG2000) and 2000 average molecular weight polycarbonate diol (PCDL 2000), heating to dissolve, heating to 100 deg.C, and dehydrating for 0.5h under vacuum degree of less than 100 Pa; cooling to 70 ℃, adding 4, 4' -diphenylmethane diisocyanate and new bismuth decanoate, stirring, reacting for 2 hours at the vacuum degree of less than 100Pa and the reaction temperature of 70 ℃ to obtain the required polyurethane prepolymer, and cooling and storing in a dark place;
mixing and stirring a photoinitiator, an active diluent, polyurethane acrylate, a silane coupling agent and a filler at 70 ℃ in a dark place, then adding the polyurethane prepolymer, heating to 80 ℃, and stirring for 1h in a dark place under the vacuum degree of less than 100 Pa; finally adding a catalyst, and continuously reacting for 1h at the vacuum degree of less than 100Pa and the reaction temperature of 70-80 ℃ to obtain the high-strength/moisture dual-curing adhesive;
and after stirring, filtering the uniformly mixed mixture, and filling the mixture into a moisture-proof package through a closed pipeline for closed storage.
In the process, 1 part of ethyl 2, 4, 6-trimethylbenzoylphosphonate, 7.5 parts of 2-phenoxyethyl acrylate, 8 parts of cyclotrimethylolpropane methylal acrylate and 4 parts of ethoxy ethyl acrylate, 5 parts of urethane acrylate (EBECRYL 8413), 1.2 parts of coupling agent (KH-550), 0.8 part of fumed silica, 72 parts of polyurethane prepolymer and 0.5 part of dimorpholinodiethyl ether; wherein the molar ratio of 4, 4' -diphenylmethane diisocyanate, PTMG2000 and PCDL 2000 in the polyurethane prepolymer is 2: 0.6: 0.4 of the total weight of the mixture; the dosage of the new bismuth decanoate is 0.2 percent of that of the polyether glycol and the 4, 4' -diphenylmethane diisocyanate.
Example 3
A high-strength ultraviolet/moisture dual-curing adhesive is prepared by heating and dissolving 2000 average molecular weight polytetrahydrofuran (PTMG2000) and 2000 average molecular weight polycarbonate diol (PCDL 2000), heating to 100 deg.C, and dehydrating for 0.5h under vacuum degree of less than 100 Pa; cooling to 70 ℃, adding 4, 4' -diphenylmethane diisocyanate and new bismuth decanoate, stirring, reacting for 2 hours at the vacuum degree of less than 100Pa and the reaction temperature of 70 ℃ to obtain the required polyurethane prepolymer, and cooling and storing in a dark place;
mixing and stirring a photoinitiator, an active diluent, polyurethane acrylate, a silane coupling agent and a filler at 70 ℃ in a dark place, then adding the polyurethane prepolymer, heating to 80 ℃, and stirring for 1h in a dark place under the vacuum degree of less than 100 Pa; finally adding a catalyst, and continuously reacting for 1h at the vacuum degree of less than 100Pa and the reaction temperature of 70-80 ℃ to obtain the high-strength/moisture dual-curing adhesive;
and after stirring, filtering the uniformly mixed mixture, and filling the mixture into a moisture-proof package through a closed pipeline for closed storage.
In the process, 1 part of ethyl 2, 4, 6-trimethylbenzoylphosphonate, 7.5 parts of 2-phenoxyethyl acrylate, 8 parts of cyclotrimethylolpropane methylal acrylate and 4 parts of ethoxy ethyl acrylate, 5 parts of urethane acrylate (EBECRYL 8413), 1.2 parts of coupling agent (KH-550), 0.8 part of fumed silica, 72 parts of polyurethane prepolymer and 0.5 part of dimorpholinodiethyl ether; wherein the molar ratio of 4, 4' -diphenylmethane diisocyanate, PTMG2000 and PCDL 2000 in the polyurethane prepolymer is 2: 0.2: 0.8; the dosage of the new bismuth decanoate is 0.2 percent of that of the polyether glycol and the 4, 4' -diphenylmethane diisocyanate.
Comparative example 1: a high strength uv/moisture dual cure adhesive which differs from example 3 only in that the photoinitiator is not a free radical photoinitiator but a cationic photoinitiator such as ferrocenium salt with carbonyl groups on the aromatic hydrocarbon.
Comparative example 2: a high strength uv/moisture dual cure adhesive which differs from example 3 only in that no urethane acrylate is added.
The adhesives prepared in examples 1-3 and comparative examples 1-2 were respectively dispensed by a syringe of an automatic dispenser along a predetermined dispensing path to the surface of ceramic (optionally metal, plastic or glass), and then irradiated with 365nm or 405nm UV-LED lamp such as Nitride NS355L-5RLO at 500-2UV curing is generally carried out for a time of about 3s to 10 s; then pressing another base material on the adhesive, and controlling the height difference between the two base materials through a laminating machine; finally, the fitted part was left to cure completely at room temperature for about 24 hours without additional equipment and processing.
And then selecting the conventional Loctite 3542F adhesive to prepare a sample by adopting the method, but not requiring the irradiation of a UV-LED lamp, wherein the initial curing time of the Loctite 3542F sample is 1-2 h, and the attached part is completely cured after being placed at room temperature for about 24 h.
The products obtained in examples 1-3, comparative examples 1-2 and Loctite 3542F above were tested.
The test method comprises the following steps: pull strength for 5 minutes: the PC test pieces of 25mm x 100mm are crossly lapped, an adhesive layer of 2mm x 25mm x 0.1mm is coated on the lapping part, the PC test pieces are pressed for 1min with 500g of force, the drawing strength is tested at 10 min after the pressing, and the drawing speed is 50 mm/min.
Pull strength for 24 hours: two 25mm by 100mm PC test pieces are crossly lapped, an adhesive layer of 2mm by 25mm by 0.1mm is coated on the lapping part, the pressing is carried out for 1min with 500g of force, the drawing strength is tested after 24 hours from the pressing, and the drawing speed is 50 mm/min.
The data obtained from the tests are shown in table 1:
TABLE 1
As can be seen from the above experiments and table 1, the pull strength of the adhesives prepared in examples 1 to 3 is much higher than that of the conventional Loctite 3542F in 5 minutes, that is, the initial curing speed of the adhesives prepared in examples 1 to 3 is faster, so that no additional equipment or process is needed after the initial curing, and the bonded parts are completely cured after being placed at room temperature for about 24 hours;
as can be seen from the comparison of the data of example 3 with the data of comparative examples 1 and 2, the drawing strength of the cationic photoinitiator for 5 minutes is lower, and the drawing strength of the polyurethane acrylate not added for 5 minutes and the drawing strength of the polyurethane acrylate not added for 24 hours are both much lower than those of example 3, which shows that the initiator selected by the invention is a free radical initiator, the reactivity of the matched polyurethane acrylate and the corresponding isocyanate is higher, the positioning time is reduced, and the initial strength is improved.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (4)
1. The high-strength ultraviolet/moisture dual-curing adhesive is characterized by comprising the following raw materials in parts by weight:
72 parts of polyurethane prepolymer, wherein the molar ratio of 4, 4' -diphenylmethane diisocyanate, PTMG-2000 and PCDL-2000 in the polyurethane prepolymer is 2: 0.2: 0.8, the using amount of the new bismuth decanoate is 0.2 percent of the using amount of the polyether glycol and the 4, 4' -diphenylmethane diisocyanate;
the active diluent is 7.5 parts of 2-phenoxyethyl acrylate, 8 parts of cyclotrimethylolpropane methylal acrylate and 4 parts of ethoxy ethyl acrylate;
the photoinitiator is 1 part of 2, 4, 6-trimethyl benzoyl phosphonic acid ethyl ester;
the polyurethane acrylate is 5 parts of EBECRYL8413 polyurethane acrylate;
the filler is fumed silica 0.8 part;
1.2 parts of KH-550 coupling agent;
the catalyst is dimorpholinodiethylether 0.5 part.
2. The preparation method of the high-strength ultraviolet/moisture dual-curing adhesive as claimed in claim 1, is characterized by comprising the following steps: heating and dissolving a mixture of polyether diol and polyester diol, and dehydrating; cooling, adding isocyanate and an esterification catalyst, stirring for reaction to obtain a required polyurethane prepolymer, and cooling and storing in a dark place; then mixing and stirring the photoinitiator, the reactive diluent, the polyurethane acrylate, the silane coupling agent and the filler in a dark place, then adding the polyurethane prepolymer, and heating and stirring in a dark place; and finally, adding a catalyst, and reacting to obtain the high-strength/moisture dual-curing adhesive.
3. The preparation method of the high-strength ultraviolet/moisture dual-curing adhesive as claimed in claim 2, wherein when the mixture is dissolved and dehydrated, the temperature is raised to 100 ℃, and the mixture is dehydrated for 0.5 hour under the vacuum degree of less than 100 Pa.
4. The method for using the high-strength ultraviolet/moisture dual-curing adhesive as claimed in claim 1, is characterized by comprising the following steps:
(I) coating the adhesive of claim 1 on a substrate to be bonded;
(II) irradiating the coated area with ultraviolet light;
(III) laminating the substrates to be bonded; (IV) placing the parts jointed in the step (III) at room temperature until the parts are completely cured.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010130998.2A CN111286297B (en) | 2020-02-28 | 2020-02-28 | High-strength ultraviolet/moisture dual-curing adhesive and preparation method and use method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010130998.2A CN111286297B (en) | 2020-02-28 | 2020-02-28 | High-strength ultraviolet/moisture dual-curing adhesive and preparation method and use method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111286297A CN111286297A (en) | 2020-06-16 |
CN111286297B true CN111286297B (en) | 2022-07-08 |
Family
ID=71020285
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010130998.2A Active CN111286297B (en) | 2020-02-28 | 2020-02-28 | High-strength ultraviolet/moisture dual-curing adhesive and preparation method and use method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111286297B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112574710A (en) * | 2020-12-10 | 2021-03-30 | 天津斯多福新材料研发有限公司 | High-strength rapid moisture curing hot melt adhesive and preparation method thereof |
CN113045697B (en) * | 2021-02-04 | 2021-10-12 | 东莞市德聚胶接技术有限公司 | Modified acrylate oligomer and UV (ultraviolet) and moisture dual-curing pressure-sensitive adhesive |
CN113996512B (en) * | 2021-10-25 | 2023-03-31 | 国网江苏省电力有限公司检修分公司 | Construction process of acrylic acid adhesive for plugging power equipment under low-temperature condition |
TWI829267B (en) * | 2022-07-29 | 2024-01-11 | 許立雍 | Electromagnetically activated moisture reactive solid adhesive |
CN115353810B (en) * | 2022-09-08 | 2024-01-30 | 杭州之江有机硅化工有限公司 | UV and moisture dual-curing adhesive as well as preparation method and application thereof |
CN115287032A (en) * | 2022-09-09 | 2022-11-04 | 天津斯多福新材料研发有限公司 | OC adhesive for ultrathin frameless liquid crystal display and preparation method thereof |
CN116651715A (en) * | 2023-05-12 | 2023-08-29 | 佛山市奥川顺新材料实业有限公司 | Polyurethane adhesive coating film forming process |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102352176A (en) * | 2011-05-27 | 2012-02-15 | 厦门固克涂料集团有限公司 | Combination of polyurethane modified epoxy resin and modified secondary amine delayed-hardening agent as primer of polyurea elastomer |
CN103467706A (en) * | 2013-09-26 | 2013-12-25 | 烟台德邦科技有限公司 | Preparation method of high-UV activity polyurethane acrylate |
CN105802483A (en) * | 2016-03-29 | 2016-07-27 | 张家港康得新光电材料有限公司 | Dual-curing coating, preparation method and application |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19810793A1 (en) * | 1998-03-12 | 1999-09-16 | Basf Ag | Curable polyurethane polymer, dispersion based on this polymer, process for its preparation and its use |
CA2426554C (en) * | 2000-10-23 | 2011-06-21 | Henkel Kommanditgesellschaft Auf Aktien | Reactive adhesive with a low monomer content and with multistage hardening |
KR101357270B1 (en) * | 2012-03-14 | 2014-02-03 | 한국신발피혁연구원 | Primer composition for difficulty adhesion shoe material without halogen |
CN103525355B (en) * | 2013-10-16 | 2015-02-18 | 烟台德邦科技有限公司 | Ultraviolet curing adhesive for liquid crystal display television side frame and preparation method of ultraviolet curing adhesive |
CN105086916B (en) * | 2015-08-05 | 2017-10-17 | 天津沃尔提莫新材料技术股份有限公司 | A kind of double curing adhesives of high printing opacity UV moistures |
CN105255435B (en) * | 2015-10-19 | 2017-12-19 | 烟台德邦科技有限公司 | A kind of preparation method of light/wet double solidification polyurethane hot melts |
CN108929621A (en) * | 2017-05-23 | 2018-12-04 | 太仓顺如成建筑材料有限公司 | A kind of ultraviolet curing insulated paint |
-
2020
- 2020-02-28 CN CN202010130998.2A patent/CN111286297B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102352176A (en) * | 2011-05-27 | 2012-02-15 | 厦门固克涂料集团有限公司 | Combination of polyurethane modified epoxy resin and modified secondary amine delayed-hardening agent as primer of polyurea elastomer |
CN103467706A (en) * | 2013-09-26 | 2013-12-25 | 烟台德邦科技有限公司 | Preparation method of high-UV activity polyurethane acrylate |
CN105802483A (en) * | 2016-03-29 | 2016-07-27 | 张家港康得新光电材料有限公司 | Dual-curing coating, preparation method and application |
Non-Patent Citations (1)
Title |
---|
Liang, HB 等.SYNTHESIS AND PROPERTIES OF UV/MOISTURE DUAL CURABLE HYPERBRANCHED POLYURETHANE COATINGS.《ACTA POLYMERICA SINICA》.2009,(第12期),第1211-1218页. * |
Also Published As
Publication number | Publication date |
---|---|
CN111286297A (en) | 2020-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111286297B (en) | High-strength ultraviolet/moisture dual-curing adhesive and preparation method and use method thereof | |
CN112724915B (en) | Reactive polyurethane hot melt adhesive with multiple curing modes and preparation method thereof | |
CA2661812C (en) | Solid polymeric substrate having adherent resin component derived from curable silylated polyurethane composition | |
EP2794797B1 (en) | An ultraviolet-curable and moisture-curable adhesive composition | |
KR20140044868A (en) | A one-component, dual-cure adhesive for use on electronics | |
EP1601705A2 (en) | Moisture curable, radiation curable sealant composition | |
CN112143442B (en) | Water-resistant high-temperature-resistant mixed acrylate flexible ultraviolet curing adhesive and preparation method thereof | |
WO1995020611A1 (en) | Urethane adhesive compositions | |
EP1799738A1 (en) | Low volatile isocyanate monomer containing polyurethane prepolymer and adhesive system | |
KR20110105486A (en) | Ultraviolet hardening polyurethane adhesive, making method thereof, and liquid crystal displsy adhesion method using it | |
EP2948513B1 (en) | Reactive hot melt adhesive | |
JP2002309185A (en) | Actinic-radiation-curing pressure-sensitive adhesive composition | |
CN113736414B (en) | Dual-curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
CN104531045A (en) | Preparing method for reaction type polyurethane hot melt adhesive with multiple curing modes | |
EP3094682B1 (en) | Reactive hot melt adhesives with improved adhesion | |
CN114133530B (en) | Polyurethane acrylic ester with NCO reactive group and UV moisture curing adhesive with resin | |
CN110382649B (en) | Reactive hot melt polyurethane adhesives with low monomeric diisocyanate content | |
CN114921218B (en) | UV (ultraviolet) -moisture dual-curing adhesive and preparation method thereof | |
CN115181535B (en) | Ultraviolet light-moisture dual-curing polyurethane hot melt adhesive and preparation method thereof | |
CN110791245A (en) | Radiation curing adhesive composition, pressure-sensitive adhesive and protective film adhesive tape | |
WO2010061759A1 (en) | Moisture-curable hot melt adhesive | |
EP0958319A1 (en) | Unsaturated polymer polyurethane structural adhesive | |
CN113337220A (en) | High-resilience ultraviolet light and moisture dual-curing hot melt adhesive and preparation method thereof | |
CN115135676A (en) | Light-moisture-curable resin composition, adhesive for electronic component, cured product, and electronic component | |
CN116606415A (en) | Comb-type silane end-capped polyurethane polymer resin, and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |