A uv moisture dual-curing adhesive as well as a preparation method and application thereof

Abstract

This invention provides a UV-moisture dual-curing adhesive, its preparation method, and its application. The raw materials for preparing the UV-moisture dual-curing adhesive include a combination of isocyanate acrylate polymer, acrylate monomers, photoinitiator, and water-absorbing agent. The raw materials for preparing the isocyanate acrylate polymer include a combination of isocyanate, hydroxy acrylate, catalyst A, and polymerization inhibitor A. The raw materials for preparing the hydroxy acrylate include acrylate monomers and nonlinear small molecule diols. The nonlinear small molecule diol is used as a chain extender to react with the acrylate monomers to obtain the hydroxy acrylate, which is then reacted with isocyanate to obtain the isocyanate acrylate polymer. The UV-moisture dual-curing adhesive prepared using the isocyanate acrylate polymer as the main resin not only has the advantages of UV and moisture dual curing, but also has excellent comprehensive mechanical properties after curing.

Description

Technical Field

[0001] This invention belongs to the field of adhesive technology, specifically relating to a UV moisture dual-curing adhesive, its preparation method, and its application. Background Technology

[0002] UV-curable adhesives, also known as UV glue, shadowless glue, or ultraviolet glue, are one-component UV-visible light-curing modified acrylic structural adhesives. They require ultraviolet light irradiation to cure. UV adhesives not only possess advantages such as high bonding strength, high transparency, non-yellowing, non-whitening, and good weather resistance, but also have moderate viscosity, providing high strength for bonding plastics to plastics and plastics to metals. They are particularly effective for bonding, reinforcing, and strengthening metals with various plastics such as PMMA, PC, ABS, and PVC, and are widely used in industries such as microelectronics, optical communication, optoelectronics, medical, home furnishings, and aerospace.

[0003] UV adhesives have the characteristics of fast curing speed (curing can be completed in a few seconds to tens of seconds, which is beneficial to automated production lines and improves labor productivity) and solvent-free (no VOCs, which is environmentally friendly), and have been widely used and rapidly developed in recent years.

[0004] Currently, there are many studies and reports on UV adhesives. CN112608688A discloses a UV adhesive, which, by weight, comprises the following components: 20-80 parts of UV oligomer, 10-60 parts of UV functional monomer, 1-5 parts of photoinitiator, 0.1-5 parts of additives, and 1-10 parts of functional filler. The UV oligomer includes one or more of the following: polyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate, polyolefin-modified (meth)acrylate, silane-modified (meth)acrylate, and pure acrylate. The UV functional monomers are active monomers that can be polymerized by photoinitiators, including one or more of (meth)acrylic acid monomers, olefin monomers, vinyl ether monomers, and allyl monomers. The UV adhesive provided by this invention features high light transmittance, fast curing speed, tough adhesive layer, vibration resistance, good stability, good weather resistance, good insulation, high temperature resistance, waterproofing, and high hardness, making it particularly suitable for LED chip encapsulation applications. As is well known, the curing principle of UV adhesives is that the photoinitiator (or photosensitizer) in the UV-curing material absorbs ultraviolet light under ultraviolet irradiation, generating active free radicals or cations, initiating monomer polymerization, crosslinking, and grafting chemical reactions, causing the adhesive to transform from a liquid to a solid state within seconds. However, with the development of new materials, many materials are not transparent, and traditional UV adhesives, including those mentioned above, cannot solve the bonding problems of these materials.

[0005] Therefore, it is essential to develop an adhesive with excellent comprehensive mechanical properties that can be cured using both UV and moisture curing methods. CN112980337A discloses a high-temperature resistant, flame-retardant UV- and moisture-curable dual-curable adhesive and its preparation method, relating to the field of adhesives. It includes a high-temperature resistant, flame-retardant, UV- and moisture-curable dual-curable oligomer, silane-modified polyether, reinforcing filler, fumed silica, acrylic-modified siloxane monomer, dehydrating agent, coupling agent, photoinitiator, and catalyst. This invention solves the problems of poor temperature resistance, poor adhesion, and flammability of current silane-modified acrylates, achieving rapid initial strength formation under UV light for rapid positioning. Simultaneously, with triazine as the core framework and a high nitrogen content in the molecular structure, it exhibits excellent self-extinguishing flame-retardant properties, high chemical stability, and excellent resistance to light aging and weathering after curing. The cured product has a denser cross-linking density, stronger intermolecular cohesion, and superior temperature resistance and adhesion. However, the UV-moisture dual-curing adhesive provided by this invention has poor mechanical properties, making it difficult to meet the application requirements of some fields that require high mechanical strength, thus limiting its wide application.

[0006] Therefore, developing a UV-curable moisture-curing adhesive with high tensile strength, tensile shear strength, and high hardness is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a UV moisture dual-curing adhesive, its preparation method, and its application. The UV moisture dual-curing adhesive is prepared by first using a nonlinear small-molecule diol as a chain extender to obtain a hydroxy acrylate, which is then further reacted with an isocyanate to obtain an isocyanate acrylate polymer. This isocyanate acrylate polymer is used as the main resin in the UV adhesive, resulting in a UV moisture dual-curing adhesive with excellent tensile strength, tensile shear strength, and high hardness, exhibiting superior overall mechanical properties.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a UV moisture dual-curing adhesive, wherein the raw materials for preparing the UV moisture dual-curing adhesive comprise the following components in parts by weight:

[0010]

[0011] The raw materials for preparing the isocyanate acrylate polymer include the following components in parts by weight:

[0012]

[0013] The raw materials for preparing the hydroxyacrylate include acrylic monomers and nonlinear small molecule diols.

[0014] The isocyanate acrylate polymer can be 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, or 58 parts by weight, etc.

[0015] The acrylate monomers can be in quantities of 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, or 38 parts by weight.

[0016] The photoinitiator can be 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, etc.

[0017] The absorbent can be 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, or 0.9 parts by weight, etc.

[0018] The isocyanate can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, etc.

[0019] The hydroxy acrylate can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, etc.

[0020] The catalyst A can be 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, or 0.09 parts by weight, etc.

[0021] The polymerization inhibitor A can be 0.04 parts by weight, 0.06 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, or 0.35 parts by weight, etc.

[0022] The UV-moisture dual-curing adhesive provided by this invention comprises a specific number of parts of an isocyanate acrylate polymer, acrylate monomers, a photoinitiator, and a water-absorbing agent. The isocyanate acrylate polymer comprises a specific number of parts of isocyanate, hydroxy acrylate, catalyst A, and polymerization inhibitor A. The hydroxy acrylate is further defined as comprising acrylate monomers and a nonlinear small-molecule diol. First, the nonlinear small-molecule diol is used as a chain extender to react with the acrylate monomers to obtain hydroxy acrylate. Then, the obtained hydroxy acrylate is further reacted with the isocyanate to obtain the isocyanate acrylate polymer. The UV-moisture dual-curing adhesive prepared using the above-mentioned isocyanate acrylate polymer as the main resin not only has the advantage of being able to be cured by both UV and moisture curing methods, but also exhibits excellent tensile strength, tensile shear strength, and high hardness after curing, demonstrating excellent comprehensive mechanical properties.

[0023] Preferably, the acrylate monomers include a combination of monofunctional acrylate monomers and difunctional acrylate monomers.

[0024] As a preferred technical solution of the present invention, the combination of monofunctional acrylate monomers and difunctional acrylate monomers can further improve the mechanical properties of the final UV adhesive.

[0025] Preferably, the content of monofunctional acrylate monomers in the raw materials for preparing the UV moisture dual-curing adhesive is 15 to 30 parts by weight, such as 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, or 28 parts by weight.

[0026] Preferably, the monofunctional acrylate monomers include any one or a combination of at least two of the following: methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxyethyl phosphate acrylate, isobornyl acrylate, tetrahydrofuran methyl acrylate, acryloylmorpholine, or dimethacrylamide, and more preferably isobornyl acrylate and / or tetrahydrofuran methyl acrylate.

[0027] Preferably, the content of difunctional acrylate monomers in the raw materials for preparing the UV moisture dual-curing adhesive is 5 to 10 parts by weight, such as 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight.

[0028] Preferably, the bifunctional acrylate monomer includes tripropylene glycol diacrylate and / or dipropylene glycol diacrylate.

[0029] Preferably, the photoinitiator comprises any one or a combination of at least two of the following: 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO), ethyl 2,4,6-trimethylbenzoylphosphonate (TPO-L), 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone (907), 2-isopropylthioxanthone (2,4 isomer mixture) (ITX), ethyl 4-dimethylaminobenzoate (EDB), 1-hydroxy-cyclohexylphenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), benzoin dimethyl ether (BDK 651), methyl o-benzoylbenzoate (OMBB), or 4-chlorobenzophenone (CBP).

[0030] Preferably, the absorbent includes any one or a combination of at least two of TI absorbent, calcium oxide, or molecular sieve.

[0031] Preferably, the raw materials for preparing the UV moisture dual-curing adhesive further include fillers and / or coupling agents.

[0032] Preferably, the filler content in the raw materials for preparing the UV moisture dual-curing adhesive is 2 to 10 parts by weight, such as 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight.

[0033] Preferably, the filler comprises silica.

[0034] Preferably, the silica is a hydrophobic fumed silica.

[0035] Preferably, the coupling agent content in the raw materials for preparing the UV moisture dual-curing adhesive is 0.1 to 1 part by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight.

[0036] Preferably, the coupling agent includes epoxy silane coupling agents, vinyl silane coupling agents, secondary amino silane coupling agents, mercapto silane coupling agents, acryloyloxy silane coupling agents, methacryloyloxy silane coupling agents, isocyanate silane coupling agents, and more preferably epoxy silane coupling agents.

[0037] Preferably, the epoxy silane coupling agent includes γ-(2,3-epoxypropoxy)propyltrimethoxysilane and / or γ-(2,3-epoxypropoxy)propyltriethoxysilane.

[0038] Preferably, the isocyanate includes hexamethylene diisocyanate (HDI), isoflurone diisocyanate (IPDI), methylcyclohexyl diisocyanate (HTDI), and dicyclohexylmethane-4,4'-diisocyanate (HDI). 12Trimers of MDI, phenylenediamine diisocyanate (XDI), dicyclohexylmethane diisocyanate (HXDI), 2,4,4-trimethylhexamethylene diisocyanate (TMHDI), norbornene diisocyanate (NBDI), trimethyl-1,6-hexamethylene diisocyanate (TMDI), tetramethyl-isophthalamide diisocyanate (TMXDI), L-lysine diisocyanate (LDI), pentamethylmethylene diisocyanate (PDI), biuret, or trimethylpropane (TMP) adducts, or combinations of at least two of these.

[0039] Preferably, the isocyanate comprises any one or a combination of at least two of the following: HDI trimer, HDI biuret, HDI-TMP adduct, IPDI trimer, IPDI biuret, IPDI-TMP adduct, XDI trimer, XDI biuret, XDI-TMP adduct, H12MDI trimer, H12MDI biuret, H12MDI-TMP adduct, TMXDI trimer, TMXDI biuret, TMXDI-TMP adduct, LDI trimer, LDI biuret, LDI-TMP adduct, PDI trimer, PDI biuret, or PDI-TMP adduct. More preferably, it is any one or a combination of at least two of the following: XDI trimer, PDI trimer, LDI trimer, biuret, or TMP adduct. Even more preferably, it is HDI trimer and / or biuret.

[0040] Preferably, the acrylic monomers include methacrylic acid and / or acrylic acid.

[0041] Preferably, the nonlinear small molecule diol includes any one or a combination of at least two of 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, dipropylene glycol, tripropylene glycol, or tetrapropylene glycol.

[0042] Preferably, catalyst A comprises any one or a combination of at least two of organotin catalysts, organobismuth catalysts, or organozinc catalysts.

[0043] Preferably, the organotin catalyst comprises any one or a combination of at least two of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide, or octyltin oxide.

[0044] Preferably, the organic bismuth catalyst comprises any one or a combination of at least two of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, or bismuth naphthenate.

[0045] Preferably, the organozinc catalyst includes any one or a combination of at least two of zinc neodecanoate, zinc laurate, zinc isooctanoate, or zinc naphthenate.

[0046] Preferably, the polymerization inhibitor A comprises any one or a combination of at least two of hydroquinone (HQ), p-benzoquinone (PBQ), methylhydroquinone (THQ), p-hydroxyanisole (HQMME), 2-tert-butylhydroquinone (MTBHQ), 2,5-di-tert-butylhydroquinone, 5-DTBHQ, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, or methylene blue, and more preferably p-hydroxyanisole.

[0047] Preferably, the acrylic monomers include methacrylic acid and / or acrylic acid.

[0048] Preferably, the nonlinear small molecule diol includes any one or a combination of at least two of 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, dipropylene glycol, tripropylene glycol, or tetrapropylene glycol.

[0049] Preferably, the molar ratio of the acrylic monomer and the nonlinear small molecule diol is 1:(2-7), such as 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6 or 1:6.5, etc., more preferably 1:(3-5), and even more preferably 1:4.

[0050] Preferably, the raw materials for preparing the hydroxyacrylate also include any one or a combination of at least two of the following: an azeotropic agent, catalyst B, or polymerization inhibitor B.

[0051] Preferably, the catalyst B comprises p-benzenesulfonic acid.

[0052] Preferably, the azeotropic agent comprises cyclohexane.

[0053] Preferably, the polymerization inhibitor B comprises any one or a combination of at least two of hydroquinone, benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 5-DTBHQ, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, or methylene blue, and more preferably p-hydroxyanisole.

[0054] Preferably, the hydroxy acrylate is prepared by the following method, the method comprising: mixing a nonlinear small molecule diol, optionally a polymerization inhibitor B, optionally an azeotropic agent and optionally a catalyst B, adding an acrylic monomer to react, and obtaining the hydroxy acrylate;

[0055] Preferably, the reaction time is 1 to 3 hours, such as 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, or 2.8 hours.

[0056] Preferably, the reaction temperature is 90–110°C, such as 92°C, 94°C, 96°C, 98°C, 100°C, 102°C, 104°C, 106°C, or 108°C.

[0057] Preferably, the raw materials for preparing the isocyanate acrylate polymer also include stabilizers and / or antioxidants.

[0058] Preferably, the stabilizer comprises any one or a combination of at least two of acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride or trichloroacetyl chloride, and more preferably benzoyl chloride.

[0059] Preferably, the stabilizer content in the raw materials for preparing the isocyanate acrylate polymer is 0.02 to 0.2 parts by weight, such as 0.04 parts by weight, 0.06 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, or 0.18 parts by weight.

[0060] Preferably, the antioxidant content in the raw materials for preparing the isocyanate acrylate polymer is 0.01 to 0.3 parts by weight, such as 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, or 0.09 parts by weight.

[0061] Preferably, the antioxidant includes any one or a combination of at least two of the following: hindered phenolic antioxidants, hindered amine antioxidants, phosphite antioxidants, thiodipropionate antioxidants, or thiol antioxidants.

[0062] Preferably, the antioxidants include 2,6-di-tert-butyl-p-cresol (BHT or 264), β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol ester (antioxidant 1076), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (antioxidant CA), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (antioxidant 330), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (MEB), N,N'-hexamethylenebis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide (HBP), 1,3,5-tris(3,5-tert-butyl-4-hydroxybenzyl)trimethylbenzene (TBM), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanate (TBHI or antioxidant 3114). The following are all of the following: 4-hydroxydodecanoic acid oxyaniline (HLS), 4-hydroxyoctadecanoic acid oxyaniline (HSS), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (antioxidant 300), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246, abbreviated as MMB), 4,4'-di-tert-octyl diphenylamine (DOD), 1,6-hexamethylenebis(3,5-di-tert-J-yl-4-hydroxyphenyl)propionate (EBP), tris(nonylphenyl) phosphite (TNP), tris(2,4-di-tert-butylphenyl) phosphite (TBP), pentaerythritol dioctadecanyl bis(octadecyl) diphosphite (DPD), tetra(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphate, or dilaurate thiodipropionate (DLTDP)

[0063] Preferably, the isocyanate acrylate polymer is prepared by the following method, which includes: mixing hydroxy acrylate, isocyanate, polymerization inhibitor A, optionally a stabilizer and optionally an antioxidant in a solvent, adding catalyst A to react, and obtaining the isocyanate acrylate polymer.

[0064] Preferably, the mixing time is 5 to 15 minutes, such as 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, or 14 minutes.

[0065] Preferably, the reaction temperature is 40-50°C, such as 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, or 49°C.

[0066] Preferably, the reaction time is 3 to 5 hours, such as 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, or 4.8 hours.

[0067] In a second aspect, the present invention provides a method for preparing the UV moisture dual-curing adhesive as described in the first aspect, the method comprising: mixing an isocyanate acrylate polymer, an acrylate monomer, a photoinitiator, a water absorbent, optionally a filler and optionally a coupling agent to obtain the UV moisture dual-curing adhesive.

[0068] Thirdly, the present invention provides an application of the UV moisture dual-curing adhesive as described in the first aspect in opaque products.

[0069] Preferably, the opaque product includes electronic products or automobiles.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] (1) The UV-moisture dual-curing adhesive provided by the present invention comprises a combination of a specific number of isocyanate acrylate polymers, acrylate monomers, photoinitiators and water absorbents. The raw materials for preparing the isocyanate acrylate polymer are further defined as a combination of a specific number of isocyanates, hydroxy acrylates, catalysts and polymerization inhibitors. The raw materials for preparing the hydroxy acrylates include acrylate monomers and nonlinear small molecule diols. The nonlinear small molecule diols are used as chain extenders to react with the acrylate monomers to obtain hydroxy acrylates, which are then further reacted with the isocyanate to obtain the isocyanate acrylate polymer. The UV-moisture dual-curing adhesive prepared using the isocyanate acrylate polymer as the main resin has the advantage of being able to be cured by both UV and moisture curing methods. After curing, it also has excellent tensile strength, tensile shear strength and high hardness, and has excellent comprehensive mechanical properties.

[0072] (2) Specifically, the UV-moisture dual-curing adhesive provided by the present invention has a tensile shear strength of 7.84-9.46 MPa, a tensile strength of 7.15-8.93 MPa, an elongation at break of 93-117%, and a hardness of 70-78D after curing under both moisture and UV conditions. Detailed Implementation

[0073] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0074] Preparation Example 1

[0075] A hydroxyacrylate is prepared by means of: adding 40 mL of dipropylene glycol, 0.2 mL of p-hydroxyanisole, 20 mL of cyclohexane and 100 mL of p-benzenesulfonic acid to a three-necked flask, adding 10 mL of methacrylic acid dropwise, reacting at 100 °C for 2 h, purifying by liquid extraction (the extractant is composed of water, cyclohexane and dichloromethane in a mass ratio of 1:1:1), and distilling the solvent after extraction to obtain the hydroxyacrylate.

[0076] Preparation Example 2

[0077] A hydroxy acrylate, which differs from Preparation Example 1 only in that 2-ethyl-1,3-hexanediol is used instead of dipropylene glycol, while the amounts of other components and the preparation method are the same as in Preparation Example 1.

[0078] Preparation Example 3

[0079] An isocyanate acrylate polymer, comprising the following components by weight:

[0080]

[0081] The method for preparing the isocyanate acrylate polymer includes: mixing hydroxy acrylate (Preparation Example 1), isocyanate (TOLONATE, HDT-100), p-hydroxyanisole, benzoyl chloride, and antioxidant BHT for 10 min, adding an organotin catalyst (Fomrez, UL-28), and reacting at 45°C for 3 h to obtain the isocyanate acrylate polymer.

[0082] Preparation Example 4

[0083] An isocyanate acrylate polymer, which differs from Preparation Example 3 only in that the hydroxy acrylate obtained in Preparation Example 2 is used instead of the hydroxy acrylate obtained in Preparation Example 1, while the other components, amounts and preparation methods are the same as in Preparation Example 3.

[0084] Comparative Preparation Example 1

[0085] A hydroxy acrylate, which differs from Preparation Example 1 only in that 1,6-hexanediol is used instead of dipropylene glycol, while the amounts of other components and the preparation method are the same as in Preparation Example 1.

[0086] Comparative Preparation Example 2

[0087] An isocyanate acrylate polymer, which differs from Preparation Example 3 only in that the hydroxy acrylate obtained in Comparative Preparation Example 1 is used instead of the hydroxy acrylate obtained in Preparation Example 1, while the other components, amounts and preparation methods are the same as in Preparation Example 3.

[0088] Comparative preparation example 3

[0089] An isocyanate acrylate polymer, which differs from Preparation Example 3 only in that hydroxyethyl methacrylate is used instead of the hydroxyacrylate obtained in Preparation Example 1, while the other components, amounts and preparation methods are the same as in Preparation Example 3.

[0090] Example 1

[0091] A UV moisture-curing dual-curing adhesive, comprising the following components by weight:

[0092]

[0093] The preparation method of the UV moisture dual-curing adhesive includes: mixing isocyanate acrylate polymer (preparation example 3), isoborneol acrylate, dipropylene glycol diacrylate, photoinitiator TPO, photoinitiator 184, TI water absorbent, silica and silane coupling agent (Silquest A-187) to obtain the UV moisture dual-curing adhesive.

[0094] Example 2

[0095] A UV moisture-curing dual-curing adhesive, comprising the following components by weight:

[0096]

[0097]

[0098] The preparation method of the UV moisture dual-curing adhesive is the same as that in Example 1.

[0099] Example 3

[0100] A UV moisture-curing dual-curing adhesive, comprising the following components by weight:

[0101]

[0102] The preparation method of the UV moisture dual-curing adhesive is the same as that in Example 1.

[0103] Example 4

[0104] A UV moisture dual-curing adhesive, which differs from Example 1 only in that the isocyanate acrylate polymer obtained in Preparation Example 4 is used instead of the isocyanate acrylate polymer obtained in Preparation Example 3, while the other components, amounts and preparation methods are the same as in Example 1.

[0105] Example 5

[0106] A UV moisture dual-curing adhesive differs from Example 1 only in that isoborneol acrylate is not added, and the amount of dipropylene glycol diacrylate added is 40 parts by weight. The other components, dosages, and preparation methods are the same as in Example 1.

[0107] Example 6

[0108] A UV moisture dual-curing adhesive differs from Example 1 only in that it does not contain dipropylene glycol diacrylate, and the amount of isoborneol acrylate added is 40 parts by weight. The other components, dosages, and preparation methods are the same as in Example 1.

[0109] Example 7

[0110] A UV moisture dual-curing adhesive, which differs from Example 1 only in that isobutyl acrylate is used instead of isoborneol acrylate, while the other components, dosages and preparation methods are the same as in Example 1.

[0111] Example 8

[0112] A UV moisture dual-curing adhesive differs from Example 1 only in that tripropylene glycol diacrylate is used instead of dipropylene glycol diacrylate; all other components, dosages, and preparation methods are the same as in Example 1.

[0113] Comparative Example 1

[0114] A UV moisture dual-curing adhesive, which differs from Example 1 only in that the isocyanate acrylate polymer obtained in Comparative Preparation Example 2 is used instead of the isocyanate acrylate polymer obtained in Preparation Example 3, while the other components, amounts and preparation methods are the same as in Example 1.

[0115] Comparative Example 2

[0116] A UV moisture dual-curing adhesive, which differs from Example 1 only in that the isocyanate acrylate polymer obtained in Comparative Preparation Example 3 is used instead of the isocyanate acrylate polymer obtained in Preparation Example 3, while the other components, amounts and preparation methods are the same as in Example 1.

[0117] Comparative Example 3

[0118] A UV moisture-curing dual-curing adhesive differs from Example 1 only in that it does not contain TI water-absorbing agent; all other components, dosages, and preparation methods are the same as in Example 1.

[0119] Performance testing:

[0120] The UV-moisture dual-curing adhesives obtained in the examples and comparative examples were cured under UV curing (0.5-1J, 5-10s) and 7-day moisture curing conditions, and then tested.

[0121] (1) Tensile strength, tensile shear strength and elongation at break: tested in accordance with the standard of HJ / T 4363-2012;

[0122] (2) Shore D hardness: The test shall be conducted in accordance with the test method provided in DIN 53505-2020 Test for hardness of Shore A and Shore D rubber.

[0123] The UV moisture dual-curing adhesives provided in the examples and comparative examples were tested according to the above test methods. The test results are shown in Table 1.

[0124] Table 1

[0125]

[0126]

[0127] As can be seen from the data in Table 1, the UV moisture dual-curing adhesive provided by the present invention has excellent tensile strength, tensile shear strength and high hardness after curing, and has excellent comprehensive mechanical properties.

[0128] Specifically, the UV-moisture dual-curing adhesives obtained in Examples 1-8 have a tensile shear strength of 7.84-9.46 MPa, a tensile strength of 7.15-8.93 MPa, an elongation at break of 93-117%, and a hardness of 70-78D after moisture and UV dual curing.

[0129] Comparing the data of Example 1 and Comparative Examples 1-2, it can be seen that the absence of the isocyanate acrylate polymer specified in this invention leads to a decrease in the tensile shear strength, tensile strength, elongation at break, and hardness of the prepared adhesive after curing.

[0130] Comparing the data from Example 1 and Comparative Example 3, it can also be seen that the tensile shear strength, tensile strength, elongation at break, and hardness of the adhesive prepared without the addition of TI water-absorbing agent all decreased.

[0131] Further comparison of the data from Examples 1 and 5-6 shows that using acrylate monomers with a single functionality also has a certain impact on the mechanical properties of the cured adhesive film.

[0132] The applicant declares that this invention illustrates a UV moisture-curing dual-curing adhesive, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials in the product of this invention, additions of auxiliary components, and selection of specific methods, all fall within the protection and disclosure scope of this invention.

Claims

1. A UV-moisture dual-curing adhesive, characterized by, The raw materials for preparing the UV moisture dual-curing adhesive include the following components in parts by weight: 40-60 parts by weight of isocyanate acrylate polymer 20-40 parts by weight of acrylate monomers 2-10 parts by weight of photoinitiator 0.1 to 1 part by weight of absorbent; The raw materials for preparing the isocyanate acrylate polymer include the following components in parts by weight: Isocyanate 0.1~10 parts by weight Hydroxyacrylate 0.1~10 parts by weight Catalyst A 0.001~0.1 parts by weight Polymerization inhibitor A: 0.02~0.4 parts by weight; The raw materials for preparing the hydroxy acrylate include acrylic monomers and nonlinear small molecule diols; The nonlinear small molecule diol includes any one or a combination of at least two of 2-ethyl-1,3-hexanediol, dipropylene glycol, tripropylene glycol, or tetrapropylene glycol. The acrylate monomers include a combination of monofunctional acrylate monomers and difunctional acrylate monomers; The monofunctional acrylate monomer is isobornyl acrylate; The bifunctional acrylate monomers include dipropylene glycol diacrylate.

2. The UV moisture dual-curing adhesive according to claim 1, characterized in that, The raw materials for preparing the UV moisture dual-curing adhesive contain 15 to 30 parts by weight of monofunctional acrylate monomers.

3. The UV moisture dual-curing adhesive according to claim 1, characterized in that, The raw materials for preparing the UV moisture dual-curing adhesive contain 5 to 10 parts by weight of difunctional acrylate monomers.

4. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The photoinitiator comprises any one or a combination of at least two of the following: 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-isopropylthioxanthone (a mixture of 2,4 isomers), ethyl 4-dimethylaminobenzoate, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, or 4-chlorobenzophenone.

5. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The absorbent includes any one or a combination of at least two of TI absorbent, calcium oxide, or molecular sieve.

6. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The raw materials used in the preparation of the UV moisture dual-curing adhesive also include fillers and / or coupling agents.

7. The UV moisture dual-curing adhesive according to claim 6, characterized in that, The filler content in the raw materials for preparing the UV moisture dual-curing adhesive is 2 to 10 parts by weight.

8. The UV moisture dual-curing adhesive according to claim 6, characterized in that, The filler includes silica.

9. The UV moisture dual-curing adhesive according to claim 8, characterized in that, The silica is a hydrophobic fumed silica.

10. The UV-curable moisture-curing adhesive according to claim 6, characterized in that, The coupling agent content in the raw materials for preparing the UV moisture dual-curing adhesive is 0.1~1 parts by weight.

11. The UV-curable moisture-curing adhesive according to claim 6, characterized in that, The coupling agents include epoxy silane coupling agents, vinyl silane coupling agents, secondary amino silane coupling agents, mercapto silane coupling agents, acryloyloxy silane coupling agents, methacryloyloxy silane coupling agents, and isocyanate silane coupling agents.

12. The UV-curable moisture-curing adhesive according to claim 6, characterized in that, The coupling agent is an epoxy silane coupling agent.

13. The UV-curable moisture-curing adhesive according to claim 11, characterized in that, The epoxy silane coupling agent includes γ-(2,3-epoxypropoxy)propyltrimethoxysilane and / or γ-(2,3-epoxypropoxy)propyltriethoxysilane.

14. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The isocyanate includes any one or a combination of at least two of the following: hexamethylene diisocyanate, isoflurone diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, phenyldiisocyanate, dicyclohexylmethane diisocyanate, 2,4,4-trimethylhexane diisocyanate, norbornene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl isophenyldiisocyanate, L-lysine diisocyanate, trimers of pentamethylene diisocyanate, biuret, or trimethylpropane adducts.

15. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The isocyanate includes any one or a combination of at least two of the following: HDI trimer, HDI biuret, HDI-TMP adduct, IPDI trimer, IPDI biuret, IPDI-TMP adduct, XDI trimer, XDI biuret, XDI-TMP adduct, H12MDI trimer, H12MDI biuret, H12MDI-TMP adduct, TMXDI trimer, TMXDI biuret, TMXDI-TMP adduct, LDI trimer, LDI biuret, LDI-TMP adduct, PDI trimer, PDI biuret, or PDI-TMP adduct.

16. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The isocyanate is any one or a combination of at least two of XDI trimer, PDI trimer, LDI trimer, biuret, or TMP adduct.

17. The UV moisture dual-curing adhesive according to claim 1, characterized in that, The isocyanate is an HDI trimer and / or biuret.

18. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, Catalyst A includes any one or a combination of at least two of organotin catalysts, organobismuth catalysts, or organozinc catalysts.

19. The UV moisture dual-curing adhesive according to claim 18, characterized in that, The organotin catalyst includes any one or a combination of at least two of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide, or octyltin oxide.

20. The UV moisture dual-curing adhesive according to claim 18, characterized in that, The organic bismuth catalyst includes any one or a combination of at least two of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, or bismuth naphthenate.

21. The UV-curable moisture-curing adhesive according to claim 18, characterized in that, The organozinc catalyst includes any one or a combination of at least two of zinc neodecanoate, zinc laurate, zinc isooctanoate, or zinc naphthenate.

22. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The polymerization inhibitor A comprises any one or a combination of at least two of the following: hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 5-DTBHQ, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, or methylene blue.

23. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The polymerization inhibitor A is p-hydroxyanisole.

24. The UV moisture dual-curing adhesive according to claim 1, characterized in that, The acrylic monomers include methacrylic acid and / or acrylic acid.

25. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The molar ratio of the acrylic monomer and the nonlinear small molecule diol is 1:(2~7).

26. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The molar ratio of the acrylic monomer and the nonlinear small molecule diol is 1:(3~5).

27. The UV moisture dual-curing adhesive according to claim 1, characterized in that, The molar ratio of the acrylic monomer and the nonlinear small molecule diol is 1:

4.

28. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The raw materials for preparing the hydroxy acrylate also include any one or a combination of at least two of the following: azeotropic agent, catalyst B, or polymerization inhibitor B.

29. The UV moisture dual-curing adhesive according to claim 28, characterized in that, Catalyst B includes p-benzenesulfonic acid.

30. The UV moisture dual-curing adhesive according to claim 28, characterized in that, The azeotropic agent includes cyclohexane.

31. The UV moisture dual-curing adhesive according to claim 28, characterized in that, The polymerization inhibitor B comprises any one or a combination of at least two of the following: hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 5-DTBHQ, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, or methylene blue.

32. The UV moisture dual-curing adhesive according to claim 28, characterized in that, The polymerization inhibitor B is p-hydroxyanisole.

33. The UV moisture dual-curing adhesive according to claim 28, characterized in that, The hydroxy acrylate is prepared by the following method, which includes: mixing a nonlinear small molecule diol, optionally a polymerization inhibitor B, optionally an azeotropic agent and optionally a catalyst B, adding an acrylic monomer to react, and obtaining the hydroxy acrylate.

34. The UV moisture dual-curing adhesive according to claim 33, characterized in that, The reaction time is 1 to 3 hours.

35. The UV moisture dual-curing adhesive according to claim 33, characterized in that, The reaction temperature is 90~110℃.

36. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The raw materials for preparing the isocyanate acrylate polymer also include stabilizers and / or antioxidants.

37. The UV moisture dual-curing adhesive according to claim 36, characterized in that, The stabilizer includes any one or a combination of at least two of acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, or trichloroacetyl chloride.

38. The UV moisture dual-curing adhesive according to claim 36, characterized in that, The stabilizer is benzoyl chloride.

39. The UV moisture dual-curing adhesive according to claim 36, characterized in that, The stabilizer content in the raw materials for preparing the isocyanate acrylate polymer is 0.02~0.2 parts by weight.

40. The UV moisture dual-curing adhesive according to claim 36, characterized in that, The antioxidant content in the raw materials for preparing the isocyanate acrylate polymer is 0.01~0.1 parts by weight.

41. The UV moisture dual-curing adhesive according to claim 36, characterized in that, The antioxidants include any one or a combination of at least two of the following: hindered phenolic antioxidants, hindered amine antioxidants, phosphite antioxidants, thiodipropionate antioxidants, or thiol antioxidants.

42. The UV moisture dual-curing adhesive according to claim 36, characterized in that, The antioxidants include 2,6-di-tert-butyl-p-cresol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), N,N'-hexamethylenebis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, 1,3,5-tris(3,5-tert-butyl-4-hydroxybenzyl)trimethylbenzene, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanate. The following are any one or a combination of at least two of the following: 4-hydroxydodecanoic acid oxyaniline, 4-hydroxyoctadecanoic acid oxyaniline, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylbis(4-methyl-6-tert-butylphenol), 4,4'-di-tert-octyl diphenylamine, 1,6-hexamethylenebis(3,5-di-tert-J-yl-4-hydroxyphenyl)propionate, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol dioctadecyl diphosphite, tetra(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphate, or dilaurate thiodipropionate.

43. The UV-curable moisture-curing adhesive according to claim 1, characterized in that, The isocyanate acrylate polymer is prepared by the following method, which includes: mixing hydroxy acrylate, isocyanate, polymerization inhibitor A, optionally a stabilizer and optionally an antioxidant in a solvent, adding catalyst A to react, and obtaining the isocyanate acrylate polymer.

44. The UV moisture dual-curing adhesive according to claim 43, characterized in that, The mixing time is 5-15 minutes.

45. The UV moisture dual-curing adhesive according to claim 43, characterized in that, The reaction temperature is 40~50℃.

46. ​​The UV moisture dual-curing adhesive according to claim 43, characterized in that, The reaction time is 3-5 hours.

47. A method for preparing the UV moisture dual-curing adhesive as described in any one of claims 1 to 46, characterized in that, The preparation method includes: mixing isocyanate acrylate polymer, acrylate monomer, photoinitiator, water absorbent, optionally filler and optionally coupling agent to obtain the UV moisture dual-curing adhesive.

48. The application of a UV moisture dual-curing adhesive as described in any one of claims 1 to 46 in opaque products.

49. The application according to claim 48, characterized in that, The opaque products include electronic products or automobiles.

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