CN111117553A - UV (ultraviolet) photocuring and low-temperature thermosetting dual-curing adhesive and preparation method thereof - Google Patents
UV (ultraviolet) photocuring and low-temperature thermosetting dual-curing adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN111117553A CN111117553A CN201911420827.7A CN201911420827A CN111117553A CN 111117553 A CN111117553 A CN 111117553A CN 201911420827 A CN201911420827 A CN 201911420827A CN 111117553 A CN111117553 A CN 111117553A
- Authority
- CN
- China
- Prior art keywords
- parts
- low
- curing
- dual
- acrylate
- 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.)
- Pending
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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to an adhesive and a preparation method thereof, in particular to a UV light-curing and low-temperature thermosetting dual-curing adhesive and a preparation method thereof. The UV photocuring and low-temperature thermosetting dual-curing adhesive comprises the following components in parts by weight: 30-60 parts of polycarbonate modified polyurethane acrylate, 20-40 parts of reactive diluent, 1-6 parts of photoinitiator, 1-3 parts of thermal initiator, 0.5-10 parts of filler and 0.5-10 parts of auxiliary agent. The UV light-curing and low-temperature thermosetting dual-curing adhesive is mainly applied to bonding of lenses and infrared IR lenses in camera modules, has great significance in electronic industries such as mobile phones, flat panels and cameras, has the characteristics of dual curing and low thermosetting temperature compared with pure UV curing adhesives and high-temperature thermosetting adhesives, and realizes bonding of base materials and components with poor temperature resistance.
Description
Technical Field
The invention relates to an adhesive and a preparation method thereof, in particular to a UV light-curing and low-temperature thermosetting dual-curing adhesive and a preparation method thereof.
Background
The UV photocuring and low-temperature thermosetting dual-curing adhesive is widely applied in the electronic industry, and is particularly applied to downstream electronic products, such as products of front and rear cameras of a mobile phone and rear infrared cameras, security monitoring cameras, computer cameras, automobile cameras and the like. The currently used UV light curing adhesive or thermosetting adhesive can only realize a single curing mechanism or UV curing and high temperature thermosetting, is difficult to meet the requirement of structural design diversity of the current electronic products, and particularly has poor operability and influenced electronic product performance aiming at some camera assemblies which can not be heated and baked at high temperature and can not use pure UV curing for part of assemblies without light transmission.
Disclosure of Invention
The invention mainly aims to provide a UV photocuring and low-temperature thermosetting dual-curing adhesive and a preparation method thereof, aiming at solving the technical problems of the dual-curing adhesive, the UV photocuring and the low-temperature thermosetting adhesive, and having the advantages of strong operability, excellent bonding force, high colloid body strength and good product stability, thereby being more practical. The specific scheme is as follows:
a UV light-curing and low-temperature heat-curing dual-curing adhesive comprises the following components in parts by weight:
polycarbonate-modified urethane acrylate: 30-60 parts;
active diluent: 20-40 parts;
photoinitiator (2): 1-6 parts;
thermal initiator: 1-3 parts of
Filling: 0.5-10 parts;
auxiliary agent: 0.5-10 parts.
Further, the polycarbonate modified polyurethane acrylate is formed by condensation reaction of polycarbonate dihydric alcohol or polycarbonate polyol, isocyanate and an acrylate monomer containing terminal hydroxyl;
the diisocyanate is at least one of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the acrylate monomer containing terminal hydroxyl is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 4-hydroxy acrylate, trimethylolpropane diacrylate and pentaerythritol triacrylate.
Further, the reactive diluent is a monomer containing an acryloyloxy structure or a methacryloyloxy structure; the reactive diluent is at least one of acrylic acid, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, ethoxy ethyl acrylate, lauric acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, N-dimethylacrylamide, N-vinyl caprolactam, N-vinyl pyrrolidone, glycidyl methacrylate, tricyclodecane dimethanol diacrylate, 1, 6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, 2-hydroxyethyl methacrylate phosphate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
Further, the photoinitiator is one or more of 2,4,6- [ trimethylbenzoyl ] diphenylphosphine oxide, ethyl 2,4,6- [ trimethylbenzoyl ] phosphonate, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-propanone, 2-isopropylthioxanthone, 1-hydroxy-cyclohexyl-benzyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, methyl o-benzoylformate and 4-chlorobenzophenone.
Further, the thermal initiator is a compound with an azo or peroxide structure, and the thermal initiator is one or more of azodiisovaleronitrile, tert-butyl peroxy-2-ethylhexanoate, 4-tert-butylcyclohexyl peroxydicarbonate, lauroyl peroxide and dibenzoyl peroxide.
Further, the filler is one or more of nano-silica modified acrylate monomer or polymer, micron-sized silica and silica micropowder, and the filler is at least one of NANOCRYL A200, NANOCRYL A210, NANOCRYLA 215, NANOCRYL A216 and silica micropowder (600 meshes).
Further, the auxiliary agent comprises one or more of a defoaming agent, a wetting and leveling agent, a surfactant, a siloxane coupling agent and a thixotropic agent;
the wetting and leveling agent is at least one of BYK-300, BYK-306, BYK-307, BYK-320, BYK-331, BYK-333, BYK-371, BYK-UV3576, TEGO Wet 270, TEGO Wet 280 and TEGO 4200;
the siloxane coupling agent is at least one of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxysilane;
the thixotropic agent is at least one of R202, R974, R805 and H18.
Furthermore, the viscosity of the polycarbonate modified polyurethane acrylate is 20000-100000mPa.s/25 ℃, the number average molecular weight is 2000-10000, the molecular weight distribution coefficient is 1.31-1.42, the free NCO is less than or equal to 0.1 percent, and the average functionality is 2-4.
A preparation method of a UV photocuring and low-temperature thermosetting dual-curing adhesive comprises the following steps: 30-60 parts of polycarbonate modified urethane acrylate, 20-40 parts of reactive diluent, 1-6 parts of photoinitiator, 1-3 parts of thermal initiator, 0.5-1.0 part of wetting leveling agent, 0.5-4 parts of siloxane coupling agent, 0.5-10 parts of thixotropic agent and 0.5-10 parts of filler are defoamed, stirred and mixed, then filtered and packaged by 300 parts of stainless steel mesh and then subjected to centrifugal defoaming, wherein the defoaming rate is 1800 and 2500r/min, and the defoaming time is 2-5min, so that the UV photocuring and low-temperature thermosetting dual-curing adhesive as claimed in any one of claims 1-7 is obtained.
Further, the stirring speed is 1500-1600r/min, the stirring time is 1-3min, the temperature is controlled to be less than 20 ℃, and the storage temperature is-40 ℃ to-20 ℃.
Further, the glue curing method comprises the following steps of firstly carrying out UV curing: curing energy 3000mj/cm2(ii) a Then carrying out low-temperature thermosetting: the temperature is 70-90 deg.C, and the thermosetting time is 10-30 min.
By the technical scheme, the UV light-curing and low-temperature thermosetting dual-curing adhesive and the preparation method thereof at least have the following advantages:
the UV photocuring and low-temperature thermosetting dual-curing adhesive can be used for bonding lenses of camera modules in various electronic products and locking threads of the modules, has the advantages of strong operability, stable product performance and the like, and simultaneously overcomes the defect of poor applicability of the existing single curing mechanism or high-temperature thermosetting
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the embodiments, structures, features and effects of the optical adhesive and the preparation method thereof according to the present invention in combination with the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The invention provides a UV light-curing and low-temperature thermosetting dual-curing adhesive, which comprises the following components in parts by weight:
polycarbonate-modified urethane acrylate: 30-60 parts;
active diluent: 20-40 parts;
photoinitiator (2): 1-6 parts;
thermal initiator: 1-3 parts of
Filling: 0.5-10 parts;
auxiliary agent: 0.5-10 parts.
Preferably, the polycarbonate modified polyurethane acrylate is obtained by polymerizing polycarbonate dihydric alcohol or polycarbonate polyol and diisocyanate and then carrying out end capping by using an acrylate monomer containing a terminal hydroxyl group; viscosity of 20000-100000mPa.s/25 ℃, number average molecular weight of 2000-10000, molecular weight distribution coefficient of 1.31-1.42, free NCO less than or equal to 0.1 percent and average functionality of 2-4. This provides the host resin with the desired properties of the colloid.
The diisocyanate being 1, 6-hexaMethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (H)12MDI).
The acrylate monomer containing terminal hydroxyl is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 4-hydroxy acrylate, trimethylolpropane diacrylate and pentaerythritol triacrylate.
Preferably, the reactive diluent is a monomer having an acryloxy or methacryloxy structure and is selected from Acrylic Acid (AA), tetrahydrofurfuryl acrylate (THFA), tetrahydrofurfuryl methacrylate (THFMA), isobornyl acrylate (IBOA), ethoxyethoxyethoxyethyl acrylate (EOEOEA), Lauric Acrylate (LA), hydroxypropyl methacrylate (HPMA), hydroxyethyl methacrylate (HEMA), N-Dimethylacrylamide (DMAA), N-vinylcaprolactam (NVC), N-vinylpyrrolidone (NVP), Glycidyl Methacrylate (GMA), tricyclodecane dimethanol diacrylate (DCPDA), 1, 6-hexanediol diacrylate (HDDA), propoxylated neopentyl glycol diacrylate (NPG2PODA), 2-hydroxyethyl methacrylate phosphate (HEMAP), At least one of trimethylolpropane triacrylate (TMPTA) and pentaerythritol triacrylate (PET 3A). The method is used for adjusting the viscosity of the formula and is convenient for construction.
Preferably, the photoinitiator is at least one of 2,4,6- [ trimethylbenzoyl ] diphenylphosphine oxide (TPO), ethyl 2,4,6- [ trimethylbenzoyl ] phosphonate (TPO-L), 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-propanone (907), 2-Isopropylthioxanthone (ITX), 1-hydroxy-cyclohexyl-benzyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), methyl phthalate (OMBB) and 4-Chlorobenzophenone (CBP). This was used to initiate polymerization of the oligomers and monomers under UV light.
Preferably, the thermal initiator is at least one of azodiisovaleronitrile, tert-butyl peroxy-2-ethylhexanoate, 4-tert-butylcyclohexyl peroxydicarbonate, lauroyl peroxide and dibenzoyl peroxide. The method is used for initiating the polymerization reaction of oligomer and monomer at 70-90 ℃ within 10-30 min.
Preferably, the filler is at least one of NANOCRYL A200, NANOCRYL A210, NANOCRYL A215, NANOCRYL A216, and silica micropowder (600 mesh). The method is used for reducing the curing shrinkage of the colloid, reducing the CTE of the colloid, improving the strength of the colloid and ensuring that the colloid performance meets the application requirement.
Preferably, the auxiliary agent includes at least one of an antifoaming agent, a wetting leveling agent, a surfactant, a siloxane coupling agent, and a thixotropic agent. The wetting and leveling agent can promote the wetting of the base material in the glue construction process and increase the adhesive force to the base material; the surface active agent can activate the surface of the substrate and promote the wetting and the attachment of the colloid to the substrate; the siloxane coupling agent can form a chemical bond with the surface component of the base material to promote the adhesion of the colloid to the base material; the thixotropic agent can improve the workability of the glue and prevent unnecessary glue overflow.
The wetting and leveling agent is at least one of BYK-300, BYK-306, BYK-307, BYK-320, BYK-331, BYK-333, BYK-371, BYK-UV3576, TEGO Wet 270, TEGO Wet 280 and TEGO 4200.
The siloxane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane and gamma-methacryloxypropyltrimethoxysilane.
The thixotropic agent is at least one of R202, R974, R805 and H18.
One embodiment of the present invention provides a method for preparing a UV light curing and low temperature thermosetting dual-curing adhesive, which comprises: 30-60 parts of polycarbonate modified polyurethane acrylate, 20-40 parts of reactive diluent, 1-6 parts of photoinitiator, 1-3 parts of thermal initiator, 0.5-1.0 part of wetting leveling agent, 0.5-4 parts of siloxane coupling agent, 0.5-10 parts of thixotropic agent and 0.5-10 parts of filler, defoaming, stirring and mixing at the stirring rate of 1500-1600r/min for 1-3min, controlling the temperature to be less than 20 ℃, repeatedly stirring for 3-4 times, filtering and packaging with 300 stainless steel mesh, centrifuging and defoaming at the defoaming rate of 1800-2500r/min for 2-5min to obtain the UV photocuring and low-temperature thermosetting dual-curing adhesive.
The invention provides a polycarbonate modified urethane acrylate A, 100g of 1, 6-hexamethylene diisocyanate is taken to be put into a four-mouth flask, the stirring speed is controlled to be 300-500r/min, the temperature is controlled to be 70 +/-5 ℃, a mixture of 250g of polycarbonate dihydric alcohol or polyhydric alcohol and a proper amount of active diluent, polymerization inhibitor, catalyst and antioxidant is dripped by a constant pressure dripping funnel, the dripping speed is controlled to be 2-6 drops/second, the temperature is gradually increased to be 80 +/-5 ℃ after the dripping is finished, the reaction is carried out for 4-5 hours, the temperature is reduced to 70 ℃ after the sampling detection of NCO is 8.0-9.0 percent, the dripping time is controlled to be 1-2 hours, the temperature is increased to be 85-90 ℃ after the dripping is finished, the reaction is continued for 4-5 hours, detecting NCO to be less than or equal to 0.1 percent, and stopping the reaction to obtain the polycarbonate modified urethane acrylate A.
Another polycarbonate modified urethane acrylate B provided by one embodiment of the invention is prepared by putting 110g of isophorone diisocyanate into a four-neck flask, controlling the stirring speed to be 300-500r/min, controlling the temperature to be 70 +/-5 ℃, dripping a mixture of 260g of polycarbonate diol or polyol and a proper amount of reactive diluent, polymerization inhibitor, catalyst and antioxidant by using a constant-pressure dropping funnel, controlling the dripping speed to be 2-6 drops/second, gradually heating to 80 +/-5 ℃ after dripping is finished, reacting for 4-5 hours, cooling to 70 ℃ after sampling and detecting the NCO to be 8.0-9.0%, dripping 130g of hydroxyethyl methacrylate and a mixture of a proper amount of polymerization inhibitor and antioxidant by using the constant-pressure dropping funnel, controlling the dripping time to be 1-2 hours, heating to 85-90 ℃ after dripping is finished, continuing to react for 4-5 hours, detecting NCO to be less than or equal to 0.1 percent, and stopping the reaction to obtain the polycarbonate modified urethane acrylate B.
Example 1
The preparation method of the UV light-curing and low-temperature thermosetting dual-curing adhesive provided by the embodiment of the invention accurately weighs (uses an electronic scale with the precision of 0.01 g) the weight of the adhesive, and self-synthesizes the polycarbonate modified polyurethane acrylate A: 30g, self-synthesized polyester urethane acrylate B: 30g of the total weight of the mixture; THFA: 11g of a reaction solution; IBOA: 10g of a mixture; nano filler NANOCRYL A200: 15g, coupling agent A-174: 1.5 g; photoinitiator 1173:2.0 g; photoinitiator TPO:1.5 g; peroxydicarbonate (4-tert-butylcyclohexyl): 1.5 g; leveling agent WT 270: 0.5 g; thixotropic agent H18: 7.5 g. Stirring for 1-3min by a planetary defoaming mixer at 1500-1600r/min, controlling the temperature of the materials at 15 ℃, repeatedly stirring for 3 times, filtering and subpackaging the materials into needle tubes by a 300-mesh stainless steel net, and defoaming again by a high-speed centrifugal defoaming machine at a defoaming rate of 1800r/min for 5min to obtain the UV light-curing and low-temperature thermosetting dual-curing adhesive; the adhesive is yellowish and transparent or semitransparent, the viscosity is controlled to be 14000-20000mPa.s/25 ℃, and the thixotropic index is 5.5-6.0.
The UV light-curing and low-temperature heat-curing dual-curing adhesive provided by one embodiment of the invention is prepared by the method and comprises the following components in parts by weight:
self-synthesis of polycarbonate modified urethane acrylate a: 30g of the total weight of the mixture;
self-synthesis of polycarbonate modified urethane acrylate B: 30g of the total weight of the mixture;
reactive diluent THFA: 11g of a reaction solution;
reactive diluent IBOA: 10g of a mixture;
nanofiller NANOCRYL a 200:15g of the total weight of the mixture;
coupling agent A-174: 1.5 g;
2.0g of photoinitiator 1173;
1.5g of photoinitiator TPO;
peroxydicarbonate (4-tert-butylcyclohexyl): 1.5 g;
leveling agent WT 270: 0.5 g;
thixotropic agent H18: 7.5 g;
example 2
The preparation method of the optical adhesive provided by one embodiment of the invention accurately weighs (using an electronic scale with the precision of 0.01 g) the self-synthesized polyester type polyurethane acrylate A:20g, self-synthesized polyester urethane acrylate B: 40g of the total weight of the mixture; DMAA: 10g of a mixture; IBOA, 15 g; nanofiller NANOCRYL a 210: 10g of a mixture; coupling agent A-174: 2.0 g; photoinitiator 1173:2.5 g; photoinitiator TPO:1.0 g; peroxydicarbonate (4-tert-butylcyclohexyl): 1.6 g; leveling agent WT 270: 0.5 g; thixotropic agent H18: 8 g. Stirring for 1-3min by a planetary defoaming mixer at 1500-1600r/min, controlling the temperature of the materials at 10 ℃, repeatedly stirring for 4 times, filtering and subpackaging the materials into needle tubes by a 300-mesh stainless steel net, and defoaming again by a high-speed centrifugal defoaming machine at the defoaming rate of 2500r/min for 3min to obtain the UV light-curing and low-temperature heat-curing dual-curing adhesive; the adhesive is yellowish and transparent or semitransparent, the viscosity is controlled to be 14000-20000mPa.s/25 ℃, and the thixotropic index is 5.5-6.0.
The UV light-curing and low-temperature heat-curing dual-curing adhesive provided by one embodiment of the invention is prepared by the method and comprises the following components in parts by weight:
self-synthesis of polycarbonate modified urethane acrylate a:20g of the total weight of the mixture;
self-synthesis of polycarbonate modified urethane acrylate B: 40g of the total weight of the mixture;
reactive diluent DMAA: 10g of a mixture;
reactive diluent IBOA:15g of the total weight of the mixture;
nanofiller NANOCRYL a 210: 10g of a mixture;
coupling agent A-174: 2.0 g;
2.5g of photoinitiator 1173;
1.0g of photoinitiator TPO;
peroxydicarbonate (4-tert-butylcyclohexyl): 1.6 g;
leveling agent WT 270: 0.5 g;
thixotropic agent H18: 8g of the total weight of the mixture;
example 3
The preparation method of the optical adhesive provided by one embodiment of the invention accurately weighs (using an electronic scale with the precision of 0.01 g) the self-synthesized polyester type polyurethane acrylate A: 40g, self-synthesized polyester urethane acrylate B: 20g of the total weight of the mixture; DMAA: 9g of a mixture; 20g of IBOA; nanofiller NANOCRYL a 200: 10g of a mixture; coupling agent A-174: 1.8 g; photoinitiator 184:2.5 g; photoinitiator TPO:1.0 g; peroxydicarbonate (4-tert-butylcyclohexyl): 1.6 g; leveling agent WT 270: 0.5 g; thixotropic agent H18: 6 g. Stirring for 1-3min by a planetary defoaming mixer at 1500-1600r/min, controlling the temperature of the material to be less than 20 ℃ (important), repeatedly stirring for 3-4 times, filtering and subpackaging the material into a needle tube by a 300-mesh stainless steel net, and defoaming again by a high-speed centrifugal defoaming machine at a defoaming rate of 1800-2500r/min for 2-5min to obtain the UV light-curing and low-temperature thermosetting dual-curing adhesive; the adhesive is yellowish and transparent or semitransparent, the viscosity is controlled to be 14000-20000mPa.s/25 ℃, and the thixotropic index is 5.5-6.0.
The UV light-curing and low-temperature heat-curing dual-curing adhesive provided by one embodiment of the invention is prepared by the method and comprises the following components in parts by weight:
self-synthesis of polycarbonate modified urethane acrylate a: 40g of the total weight of the mixture;
self-synthesis of polycarbonate modified urethane acrylate B: 20g of the total weight of the mixture;
reactive diluent DMAA: 9g of a mixture;
reactive diluent IBOA:20g of the total weight of the mixture;
nanofiller NANOCRYL a 200: 10g of a mixture;
coupling agent A-174: 1.8 g;
2.5g of photoinitiator 184;
1.0g of photoinitiator TPO;
peroxydicarbonate (4-tert-butylcyclohexyl): 1.6 g;
leveling agent WT 270: 0.5 g;
thixotropic agent H18: 6g of a mixture;
example 4
The preparation method of the optical adhesive provided by one embodiment of the invention accurately weighs (using an electronic scale with the precision of 0.01 g) the self-synthesized polyester type polyurethane acrylate A: 60g of the total weight of the mixture; THFMA: 10g of a mixture; 15g of HPMA; nanofiller NANOCRYL a 210: 10g of a mixture; coupling agent A-174: 2.0 g; photoinitiator 1173:2.5 g; photoinitiator TPO:1.0 g; peroxydicarbonate (4-tert-butylcyclohexyl): 1.5 g; leveling agent WT 270: 0.5 g; thixotropic agent H18: 8 g. Stirring for 1-3min by a planetary defoaming mixer at 1500-1600r/min, controlling the temperature of the materials at 10 ℃, repeatedly stirring for 4 times, filtering and subpackaging the materials into needle tubes by a 300-mesh stainless steel net, and defoaming again by a high-speed centrifugal defoaming machine at the defoaming rate of 2500r/min for 3min to obtain the UV light-curing and low-temperature heat-curing dual-curing adhesive; the adhesive is yellowish and transparent or semitransparent, the viscosity is controlled to be 14000-20000mPa.s/25 ℃, and the thixotropic index is 5.5-6.0.
The UV light-curing and low-temperature heat-curing dual-curing adhesive provided by one embodiment of the invention is prepared by the method and comprises the following components in parts by weight:
self-synthesis of polycarbonate modified urethane acrylate a: 60g of the total weight of the mixture;
reactive diluent THFMA: 10g of a mixture;
reactive diluent HPMA:15g of the total weight of the mixture;
nanofiller NANOCRYL a 210: 10g of a mixture;
coupling agent A-174: 2.0 g;
2.5g of photoinitiator 1173;
1.0g of photoinitiator TPO;
peroxydicarbonate (4-tert-butylcyclohexyl): 1.5 g;
leveling agent WT 270: 0.5 g;
thixotropic agent H18: 8g of the total weight of the mixture;
example 5
The preparation method of the optical adhesive provided by one embodiment of the invention accurately weighs (using an electronic scale with the precision of 0.01 g) the self-synthesized polyester type polyurethane acrylate B: 60g of the total weight of the mixture; HEMA: 15g of the total weight of the mixture; IBOA, 15 g; nanofiller NANOCRYL a 200:15g of the total weight of the mixture; coupling agent A-174: 2.5 g; photoinitiator 1173:2.5 g; photoinitiator TPO:1.0 g; peroxydicarbonate (4-tert-butylcyclohexyl): 1.8 g; leveling agent WT 270: 0.5 g; thixotropic agent H18: 8 g. Stirring for 1-3min by a planetary defoaming mixer at 1500-1600r/min, controlling the temperature of the materials at 10 ℃, repeatedly stirring for 4 times, filtering and subpackaging the materials into needle tubes by a 300-mesh stainless steel net, and defoaming again by a high-speed centrifugal defoaming machine at the defoaming rate of 2500r/min for 3min to obtain the UV light-curing and low-temperature heat-curing dual-curing adhesive; the adhesive is yellowish and transparent or semitransparent, the viscosity is controlled to be 14000-20000mPa.s/25 ℃, and the thixotropic index is 5.5-6.0.
The UV light-curing and low-temperature heat-curing dual-curing adhesive provided by one embodiment of the invention is prepared by the method and comprises the following components in parts by weight:
self-synthesis of polycarbonate modified urethane acrylate B: 60g of the total weight of the mixture;
active diluent HEMA: 15g of the total weight of the mixture;
reactive diluent IBOA:15g of the total weight of the mixture;
nanofiller NANOCRYL a 200:15g of the total weight of the mixture;
coupling agent A-174: 2.5 g;
2.5g of photoinitiator 1173;
1.0g of photoinitiator TPO;
peroxydicarbonate (4-tert-butylcyclohexyl): 1.8 g;
leveling agent WT 270: 0.5 g;
thixotropic agent H18: 8g of the total weight of the mixture;
the invention takes the existing pure UV curing product and heating curing product in the market as examples, and compares the performances of the UV photocuring and low-temperature thermosetting dual-curing adhesive of examples 1-5 and comparative examples. The test equipment used for the performance evaluation test is shown in table 1, and the performance evaluation results are shown in table 2.
Table 1 test equipment for performance evaluation test
Table 2 examples 1-2 and comparative examples the results of the performance evaluation test
In the assembly process of the camera module, the use of an adhesive requires UV photocuring and low-temperature thermosetting, so as to achieve the adhesion between the lens and the base, and as can be seen from table 2, the embodiments 1 to 5 in the present invention have the following advantages compared with the commercially available products: firstly, the bonding strength to the base material is higher; secondly, the water absorption rate is low; thirdly, the anti-aging performance is excellent, the cold and hot impact resistance is high, and the glue is not abnormal after the double 85 test. Therefore, the glue not only meets the requirements on the curing process, but also meets the requirements on the performance of the glue, and the bonding reliability between the components is improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. The UV photocuring and low-temperature thermosetting dual-curing adhesive is characterized by comprising the following components in parts by weight:
polycarbonate-modified urethane acrylate: 30-60 parts;
active diluent: 20-40 parts;
photoinitiator (2): 1-6 parts;
thermal initiator: 1-3 parts of
Filling: 0.5-10 parts;
auxiliary agent: 0.5-10 parts.
2. The UV light-curable and low-temperature heat-curable dual-curing adhesive according to claim 1, wherein the polycarbonate modified polyurethane acrylate is prepared by condensation reaction of polycarbonate diol or polycarbonate polyol, isocyanate and an acrylate monomer containing a terminal hydroxyl group;
the diisocyanate is at least one of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the acrylate monomer containing terminal hydroxyl is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 4-hydroxy acrylate, trimethylolpropane diacrylate and pentaerythritol triacrylate.
3. The UV photocuring and low-temperature thermosetting dual-curing adhesive as claimed in claim 1, wherein the reactive diluent is a monomer containing an acryloxy or methacryloxy structure; the reactive diluent is at least one of acrylic acid, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, ethoxy ethyl acrylate, lauric acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, N-dimethylacrylamide, N-vinyl caprolactam, N-vinyl pyrrolidone, glycidyl methacrylate, tricyclodecane dimethanol diacrylate, 1, 6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, 2-hydroxyethyl methacrylate phosphate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
4. The UV photocurable and low temperature thermosetting dual cure adhesive according to claim 1, wherein the photoinitiator is one or more of 2,4,6- [ trimethylbenzoyl ] diphenylphosphine oxide, ethyl 2,4,6- [ trimethylbenzoyl ] phosphonate, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-propanone, 2-isopropylthioxanthone, 1-hydroxy-cyclohexyl-benzyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, methyl o-benzoylformate and 4-chlorobenzophenone.
The thermal initiator is a compound with an azo or peroxide structure, and is one or more of azodiisovaleronitrile, tert-butyl peroxy-2-ethylhexanoate, peroxydicarbonate (4-tert-butylcyclohexyl), lauroyl peroxide and dibenzoyl peroxide.
5. The UV light-curable and low-temperature heat-curable dual-curing adhesive as claimed in claim 1, wherein the filler is one or more of nano-silica modified acrylate monomer or polymer, micron-sized silica and silica micropowder, and the filler is at least one of NANOCRYL A200, NANOCRYL A210, NANOCRYL A215, NANOCRYL A216 and silica micropowder (600 mesh).
6. The UV light-curable and low-temperature heat-curable dual-curing adhesive as claimed in claim 1, wherein the auxiliary agent comprises one or more of an antifoaming agent, a wetting and leveling agent, a surfactant, a siloxane coupling agent and a thixotropic agent;
the wetting and leveling agent is at least one of BYK-300, BYK-306, BYK-307, BYK-320, BYK-331, BYK-333, BYK-371, BYK-UV3576, TEGO Wet 270, TEGO Wet 280 and TEGO 4200;
the siloxane coupling agent is at least one of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxysilane;
the thixotropic agent is at least one of R202, R974, R805 and H18.
7. The UV photocuring and low-temperature thermosetting dual-curing adhesive as claimed in claim 2, wherein the viscosity of the polycarbonate modified polyurethane acrylate is 20000-100000mPa.s/25 ℃, the number average molecular weight is 2000-10000, the molecular weight distribution coefficient is 1.31-1.42, the free NCO is less than or equal to 0.1%, and the average functionality is 2-4.
8. A preparation method of a UV photocuring and low-temperature thermosetting dual-curing adhesive is characterized by comprising the following steps: 30-60 parts of polycarbonate modified urethane acrylate, 20-40 parts of reactive diluent, 1-6 parts of photoinitiator, 1-3 parts of thermal initiator, 0.5-1.0 part of wetting leveling agent, 0.5-4 parts of siloxane coupling agent, 0.5-10 parts of thixotropic agent and 0.5-10 parts of filler are defoamed, stirred and mixed, then filtered and packaged by 300 parts of stainless steel mesh and then subjected to centrifugal defoaming, wherein the defoaming rate is 1800 and 2500r/min, and the defoaming time is 2-5min, so that the UV photocuring and low-temperature thermosetting dual-curing adhesive as claimed in any one of claims 1-7 is obtained.
9. The method as claimed in claim 8, wherein the stirring speed is 1500-.
10. The preparation method of the UV light-curable and low-temperature heat-curable dual-curing adhesive according to claim 8, wherein the glue is cured by first performing UV curing: curing energy 3000mj/cm2(ii) a Then carrying out low-temperature thermosetting: the temperature is 70-90 deg.C, and the thermosetting time is10-30min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911420827.7A CN111117553A (en) | 2019-12-31 | 2019-12-31 | UV (ultraviolet) photocuring and low-temperature thermosetting dual-curing adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911420827.7A CN111117553A (en) | 2019-12-31 | 2019-12-31 | UV (ultraviolet) photocuring and low-temperature thermosetting dual-curing adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111117553A true CN111117553A (en) | 2020-05-08 |
Family
ID=70507528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911420827.7A Pending CN111117553A (en) | 2019-12-31 | 2019-12-31 | UV (ultraviolet) photocuring and low-temperature thermosetting dual-curing adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111117553A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112049991A (en) * | 2020-08-27 | 2020-12-08 | 湖南创瑾科技有限公司 | High-pressure plastic pipeline and preparation method thereof |
| CN112851872A (en) * | 2020-12-31 | 2021-05-28 | 烟台泰盛精化科技有限公司 | UV gasket adhesive and preparation method thereof |
| CN113388358A (en) * | 2021-06-21 | 2021-09-14 | 无锡博加电子新材料有限公司 | UV thermosetting dual-curing metal substrate adhesive |
| CN115717043A (en) * | 2022-11-02 | 2023-02-28 | 佛山阳光逸采涂料科技有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
| CN117229750A (en) * | 2023-09-18 | 2023-12-15 | 道尔化成电子材料(上海)有限公司 | Ultraviolet light curing polyurethane acrylate adhesive for lenses and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925062A (en) * | 2011-08-12 | 2013-02-13 | 汉高股份有限公司 | Optically-transparent dual-curing adhesive |
| CN103031104A (en) * | 2011-08-05 | 2013-04-10 | Dic株式会社 | Resin composition for UV-curable adhesive, adhesive and laminate |
| WO2015198493A1 (en) * | 2014-06-23 | 2015-12-30 | Arkema France | Urethane acrylate polymers with unique physical properties |
| CN106833498A (en) * | 2017-02-24 | 2017-06-13 | 广州回天新材料有限公司 | One kind sealing marine glue and its preparation method and application |
-
2019
- 2019-12-31 CN CN201911420827.7A patent/CN111117553A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031104A (en) * | 2011-08-05 | 2013-04-10 | Dic株式会社 | Resin composition for UV-curable adhesive, adhesive and laminate |
| CN102925062A (en) * | 2011-08-12 | 2013-02-13 | 汉高股份有限公司 | Optically-transparent dual-curing adhesive |
| WO2015198493A1 (en) * | 2014-06-23 | 2015-12-30 | Arkema France | Urethane acrylate polymers with unique physical properties |
| CN106833498A (en) * | 2017-02-24 | 2017-06-13 | 广州回天新材料有限公司 | One kind sealing marine glue and its preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112049991A (en) * | 2020-08-27 | 2020-12-08 | 湖南创瑾科技有限公司 | High-pressure plastic pipeline and preparation method thereof |
| CN112851872A (en) * | 2020-12-31 | 2021-05-28 | 烟台泰盛精化科技有限公司 | UV gasket adhesive and preparation method thereof |
| CN113388358A (en) * | 2021-06-21 | 2021-09-14 | 无锡博加电子新材料有限公司 | UV thermosetting dual-curing metal substrate adhesive |
| CN115717043A (en) * | 2022-11-02 | 2023-02-28 | 佛山阳光逸采涂料科技有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
| CN117229750A (en) * | 2023-09-18 | 2023-12-15 | 道尔化成电子材料(上海)有限公司 | Ultraviolet light curing polyurethane acrylate adhesive for lenses and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111117553A (en) | UV (ultraviolet) photocuring and low-temperature thermosetting dual-curing adhesive and preparation method thereof | |
| TWI577773B (en) | Liquid optical adhesive compositions | |
| EP2928974B1 (en) | Liquid optical adhesive compositions | |
| CN103748488B (en) | Polarizer | |
| CN110467890B (en) | Pressure-sensitive adhesive tape, method for producing same, and resin composition for producing pressure-sensitive adhesive tape | |
| CN108587484A (en) | A kind of optical film adhesive for being bonded entirely and its preparation method and application and based on its optical film | |
| CN102167962B (en) | Photocuring adhesive used for adhering optic glass lenses and preparation method thereof | |
| CN105602515B (en) | A kind of ultraviolet curing transfer adhesive and preparation method and application | |
| CN102010672B (en) | UV (Ultraviolet)-cured pressure-sensitive adhesive for LCD (Liquid Crystal Display) polarizer and preparation method thereof | |
| EP3071612B1 (en) | Liquid optical adhesive compositions | |
| CN107163903A (en) | Optical adhesive and preparation method thereof | |
| CN103184029A (en) | Light curing adhesive for splicing capacitive touch screen and preparation method of light curing adhesive | |
| CN113372824B (en) | Water-impact-resistant high-viscosity UV (ultraviolet) viscosity-reducing adhesive and preparation method and application thereof | |
| CN109096441A (en) | A kind of OCA resin combination, OCA adhesive tape and preparation method thereof | |
| TWI829805B (en) | Adhesive sheet, manufacturing method thereof, and image display device manufacturing method | |
| CN114141896A (en) | Composite material for front plate or back plate of photovoltaic module and preparation method and application thereof | |
| CN114350266A (en) | Liquid optical cement and preparation method and application method thereof | |
| KR20080093508A (en) | Manufacturing method of acryl pressure sensitive adhesive for polarizing film | |
| JP4915694B2 (en) | Adhesive composition | |
| KR102147778B1 (en) | Adhesive composition and adhesive sheet for optical use | |
| CN114181660B (en) | Ultraviolet light curing adhesive composition for MiniLED packaging and preparation method and application thereof | |
| CN115678483A (en) | Light-cured pressure-sensitive adhesive for water-gel film and preparation method thereof | |
| KR100934272B1 (en) | Manufacturing method of acrylic pressure sensitive adhesive, acrylic pressure sensitive adhesive and polarizing plate of display element using same | |
| CN116875228B (en) | Environment-friendly ultraviolet-resistant OCA optical cement and preparation method thereof | |
| KR102545923B1 (en) | Double hardening adhesive composition, method for producing the same, pressure-sensitive adhesive protective tape using the same, method for protecting the surface of an adherend |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200508 |