Ultraviolet curing adhesive system for gluing syringe needle and preparation method and application of ultraviolet curing adhesive system

Abstract

The invention relates to the technical field of adhesives, and discloses an ultraviolet curing adhesive system for gluing syringe needles and a preparation method and application of the ultraviolet curing adhesive system for gluing syringe needles, and the adhesive system comprises the following components which are lucifugal and independently preserved: 60-80 parts by weight of an acrylate functional monomer; 1-5 parts by weight of a photoinitiator; the prepolymer comprises 45-55 parts by weight of epoxy resin, 15-25 parts by weight of acrylic acid or methacrylic acid and 35-45 parts by weight of triphenylphosphine, wherein the epoxy resin, the acrylic acid or methacrylic acid and the triphenylphosphine are kept away from light and are respectively and independently stored; and 1-5 parts by weight of other functional auxiliary agents. The ultraviolet curing adhesive system has the characteristics of strong bonding force, fast curing and excellent mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and particularly to an ultraviolet light-curing adhesive system for syringe needle bonding, a preparation method thereof, and an application thereof. Background Art

[0002] Ultraviolet light curing is a process in which, under the irradiation of high-energy ultraviolet (UV) light (wavelength 200 - 450 nm), a photoinitiator absorbs the UV light to generate active free radicals or cations, which initiate a chain polymerization reaction of UV oligomers and active diluent molecules, causing the liquid-phase system to polymerize and crosslink to cure. Compared with thermal curing technology, UV light curing is an efficient, energy-saving, and environmentally friendly new technology, with advantages such as fast curing speed, low temperature, low energy consumption, safety and environmental protection, and excellent coating performance. With the increasing attention of people to environmental protection and energy conservation and emission reduction, the UV light curing technology has developed rapidly. In the past 5 - 10 years, the annual growth rate of the production and consumption of UV raw materials (mainly referring to resins and monomers) in China has exceeded 20%, and many research institutions and chemical companies have started to research and develop UV raw materials, UV glues, coatings, inks, etc.

[0003] Medical needle adhesives are involved in the bonding of stainless steel needles and plastic syringes in medical devices such as medical syringes and infusion sets. The most commonly used pre-filled syringes currently are a new type of drug packaging form composed of a hollow syringe barrel (which can be optionally equipped with a pre-connected needle), a rubber piston, a needle cap or a cone cap, and a push rod. Among them, the syringe barrel and the needle are generally bonded together by an ultraviolet light-curing adhesive. The adhesive generally consists of resin, reactive monomer, photoinitiator, prepolymer, inhibitor, and other additives. Among them, methacrylate monomers have excellent biosecurity and free radical reaction activity, making them widely used in bonding materials. However, there are also some problems in the use of this monomer. First, in the ultraviolet light-curing system, the crosslinking degree of the prepolymer is small and the cohesive strength is insufficient; second, acrylate is a polar macromolecular polymer with poor wettability to the metal surface, and there will be a problem of insufficient bonding strength when the acrylate adhesive is used on metal. The epoxy resin backbone structure contains ether groups and has a strong adhesion to the surface of substrates such as metal, and is an important UV-curing adhesive material, but it also has the disadvantages of slow curing speed and high curing temperature. Summary of the Invention

[0004] The object of the present invention is to overcome the defects of the commonly used epoxy needle glue in the prior art, such as small crosslinking degree of the prepolymer, insufficient cohesive strength, and insufficient bonding strength, and to provide an ultraviolet light-curing adhesive system for syringe needle bonding, a preparation method thereof, and an application thereof. The ultraviolet light-curing adhesive system has the characteristics of "strong bonding force", "fast curing", and "excellent mechanical properties".

[0005] To achieve the above object, a first aspect of the present invention provides an ultraviolet curable adhesive system for syringe needle bonding, wherein the adhesive system includes the following components that are light - protected and stored independently:

[0006] 60 - 80 parts by weight of acrylate functional monomers;

[0007] 1 - 5 parts by weight of photoinitiator;

[0008] 15 - 30 parts by weight of prepolymer, and the prepolymer includes 45 - 55 parts by weight of epoxy resin, 15 - 25 parts by weight of acrylic acid or methacrylic acid, and 35 - 45 parts by weight of triphenylphosphine that are light - protected and stored independently;

[0009] 1 - 5 parts by weight of other functional adjuvants.

[0010] A second aspect of the present invention provides a preparation method of the above - mentioned ultraviolet curable adhesive system, wherein the preparation method includes: mixing acrylate functional monomers, photoinitiator, prepolymer and other functional adjuvants under light - protected conditions to obtain the ultraviolet curable adhesive system.

[0011] A third aspect of the present invention provides an application of the above - mentioned ultraviolet curable adhesive system as a needle glue for sterile syringes in the production and preparation of disposable sterile syringe needles.

[0012] Through the above technical solutions, for the requirements of firm bonding of medical needles, such as disposable sterile syringes, the acrylate ultraviolet curable adhesive system of the present invention has the characteristics of convenient operation, firm bonding and good chemical resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is the infrared spectrum of prepolymer 1 prepared in Preparation Example 1 of the present invention;

[0014] Figure 2 is the infrared spectrum of prepolymer 4 prepared in Preparation Example 4 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0016] As described above, the first aspect of the present invention provides an ultraviolet curable adhesive system for syringe needle bonding, wherein the adhesive system comprises the following components stored separately and protected from light:

[0017] 60 - 80 parts by weight of acrylate functional monomer;

[0018] 1 - 5 parts by weight of photoinitiator;

[0019] 15 - 30 parts by weight of prepolymer, the prepolymer comprising 45 - 55 parts by weight of epoxy resin, 15 - 25 parts by weight of acrylic acid or methacrylic acid, and 35 - 45 parts by weight of triphenylphosphine stored separately and protected from light;

[0020] 1 - 5 parts by weight of other functional adjuvants.

[0021] The inventors of the present invention have found that in the present invention, a prepolymer with an interpenetrating network structure is introduced into the ultraviolet curable adhesive system, which greatly enhances the wetting effect and chemical bond action of the adhesive, achieves the effects of rapid curing and increased strength, and effectively improves the performance of the cured product and the use efficiency of the adhesive. After curing, it has high bonding strength, small volume shrinkage, excellent heat resistance and solvent resistance, and can be used as a needle glue for sterile syringes.

[0022] According to the present invention, preferably, the adhesive system comprises the following components stored separately and protected from light: 65 - 77 parts by weight of acrylate functional monomer, 2 - 5 parts by weight of photoinitiator, 17 - 28 parts by weight of prepolymer, and 3 - 5 parts by weight of other functional adjuvants. In the present invention, limiting the amounts of the respective components within the aforementioned ranges can endow the ultraviolet curable adhesive system with the advantages of high strength and high stability.

[0023] According to the present invention, the preparation method of the prepolymer comprises: under the condition of the presence of triphenylphosphine, stirring epoxy resin and acrylic acid or methacrylic acid at 100 - 110 °C for 4 - 5 hours under nitrogen and light - protected conditions, and then discharging to obtain the prepolymer.

[0024] In the present invention, the prepolymer is an interpenetrating network prepolymer.

[0025] According to the present invention, the epoxy resin comprises bisphenol A epoxy resin represented by formula (1) or epoxy novolac resin represented by formula (2);

[0026] wherein, n 1 is 15 - 30;

[0027] wherein, n is 15 - 30.

[0028] In the present invention, preferably, in formula (1), n 1 is 18 - 23, more preferably 20.

[0029] In the present invention, preferably, in formula (2), n is 18 - 23, more preferably 20.

[0030] According to the present invention, the acrylate is selected from at least two of trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, hexanediol methoxy monoacrylate, glycerol methoxy monoacrylate, ethoxylated trimethylol diacrylate, ethoxylated neopentyl glycol methoxy monoacrylate, trimethylolpropane triacrylate, methyl hydroxyacrylate, hydroxyethyl acrylate, methyl hydroxyethyl acrylate, and 2 - hydroxyethyl acrylate;

[0031] Preferably, the acrylate is selected from at least two of trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, hexanediol methoxy monoacrylate, glycerol methoxy monoacrylate, ethoxylated trimethylol diacrylate, ethoxylated neopentyl glycol methoxy monoacrylate, and trimethylolpropane triacrylate.

[0032] According to the present invention, the photoinitiator is selected from one or more of benzoin methyl ether, benzoin ethyl ether, benzoin n - butyl ether, dimethoxyacetophenone, diethoxyacetophenone, 2 - hydroxy - 2 - methyl - p - hydroxyethoxy phenylacetone, 2 - methyl - 1 - (4 - methylthiophenyl)-2 - morpholin - 1 - propanone, 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinobenzylphenyl)butanone, hydroxycyclohexyl phenyl ketone, hydroxy dimethyl acetophenone, 2 - hydroxy - 2 - methylphenyl propane - 1 - one, trimethylbenzoyl - ethoxy - phenyl phosphine oxide, trimethylbenzoyl - diphenyl phosphine oxide, bis(trimethylbenzoyl)phenyl phosphine oxide, diphenyl(2,4,6 - trimethylbenzoyl)phosphine oxide, phenyl bis(2,4,6 - trimethylbenzoyl)phosphine oxide, 2 - hydroxy - 2 - methyl - 1 - phenylpropanone, and 2,2 - dimethoxy - 2 - phenylacetophenone.

[0033] According to the present invention, preferably, the photoinitiator is selected from one or more of benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether, dimethoxy phenyl acetophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone, 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-propanone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl) butanone, hydroxy cyclohexyl phenyl ketone, hydroxy dimethyl acetophenone, 2-hydroxy-2-methylphenyl propane-1-one, trimethylbenzoyl-ethoxy-phenyl phosphine oxide, trimethylbenzoyl-diphenyl phosphine oxide, and bis(trimethylbenzoyl)phenyl phosphine oxide.

[0034] According to the present invention, the other functional adjuvants include one or more of antioxidants, adhesion promoters, and co-initiators.

[0035] According to the present invention, the antioxidant is a hindered phenol and / or p-benzoquinone.

[0036] According to the present invention, the adhesion promoter is 3-(trimethoxysilyl)propyl methacrylate (KH-570) and / or glycidoxypropyltrimethoxysilane (KH-560).

[0037] According to the present invention, the co-initiator is N,N-dimethylaminomethyl acrylate and / or p-dimethylaminobenzoate.

[0038] The second aspect of the present invention provides a method for preparing the ultraviolet curable adhesive system as described above, characterized in that the preparation method includes: mixing acrylate functional monomers, photoinitiators, prepolymers, and other functional adjuvants under light-shielded conditions to obtain an ultraviolet curable adhesive system.

[0039] According to the present invention, the conditions for mixing include: mixing and stirring under light shielding for 2-3 hours under the conditions of a vacuum degree of -0.1 MPa to -0.01 MPa and a rotation speed of 800-1000 revolutions per minute.

[0040] The third aspect of the present invention provides an application of the ultraviolet curable adhesive system as described above in the production and preparation of disposable sterile syringe needles as the needle glue for sterile syringes.

[0041] The present invention will be described in detail below through examples.

[0042] In the following examples and comparative examples:

[0043] The viscosity was measured by the method of GB / T 2794-1995;

[0044] The tensile modulus and tensile adhesion strength were measured by the method of GB / T 7124-2008;

[0045] The linear curing shrinkage rate was measured by a displacement experiment.

[0046] All the reagents used were commercially available. All kinds of acrylate functional monomers and their synthetic reagents were purchased from Innochem Co., Ltd.

[0047] Room temperature refers to 25 °C.

[0048] Preparation Example 1

[0049] 50 parts by weight of bisphenol A epoxy resin represented by formula (1) (wherein n 1 is 20), 20 parts by weight of acrylic acid, and 40 parts by weight of triphenylphosphine were respectively added to a three-necked flask. Under nitrogen protection and in the dark, the temperature was slowly raised to 105 °C, and after mechanical stirring at 600 rpm for 4 hours, the temperature was lowered to obtain a colorless viscous liquid prepolymer 1.

[0050] Among them, Figure 1 is the infrared spectrum of prepolymer 1. Figure 1 In it, at 2965 cm -1 is the stretching vibration peak of -CH 2 ; the absorption peak appearing at 1735 cm -1 is the stretching vibration peak of the ester group; the absorption peaks at 1465 cm -1 and 1410 cm -1 are the alkyl bending vibration peaks; the absorption peak appearing at 1270 cm -1 represents the in-plane deformation vibration of -OH; the absorption peaks between 1000 cm -1 and 1200 cm -1 correspond to the stretching vibrations of C-C-C and C-O-C; the absorption peaks between 800 cm -1 and 1000 cm -1 are the out-of-plane bending vibration peak groups of C-H.

[0051] Preparation Example 2

[0052] 50 parts by weight of epoxy novolac resin represented by formula (2) (wherein n is 20), 20 parts by weight of acrylic acid, and 40 parts by weight of triphenylphosphine were respectively added to a three-necked flask. Under nitrogen protection and in the dark, the temperature was slowly raised to 105 °C, and after mechanical stirring at 600 rpm for 4 hours, the temperature was lowered to obtain a colorless viscous liquid prepolymer 2.

[0053] Preparation Example 3

[0054] 50 parts by weight of bisphenol A epoxy resin represented by formula (1) (wherein n 150 parts by weight of the epoxy novolak resin represented by the formula (2) (wherein n is 20), 20 parts by weight of methacrylic acid, and 40 parts by weight of triphenylphosphine were respectively added to a three-necked flask, protected by nitrogen, shielded from light, slowly heated to 105 °C, mechanically stirred at 600 rpm for 4 hours, and then cooled to obtain a colorless viscous liquid prepolymer 4.

[0055] Preparation Example 4

[0056] 50 parts by weight of the epoxy novolak resin represented by the formula (2) (wherein n is 20), 20 parts by weight of methacrylic acid, and 40 parts by weight of triphenylphosphine were respectively added to a three-necked flask, protected by nitrogen, shielded from light, slowly heated to 105 °C, mechanically stirred at 600 rpm for 4 hours, and then cooled to obtain a colorless viscous liquid prepolymer 4.

[0057] Among them, Figure 2 is the infrared spectrum of prepolymer 4. Figure 2 In, the stretching vibration peaks of -OH overlap between 3060 cm -1 and 3550 cm -1 ; the stretching vibration peak at 2928 cm -1 is for -CH 2 ; the absorption peak appearing at 1710 cm -1 is the overlapping stretching vibration peak of the ester group; the alkyl bending vibration peaks are between 1460 cm -1 and 1395 cm -1 ; the absorption peak appearing at 1247 cm -1 represents the in-plane deformation vibration of -OH; the absorption peaks between 1000 cm -1 and 1200 cm -1 correspond to the stretching vibrations of C-C-C and C-O-C; the absorption peaks at 800 cm -1 and 900 cm -1 are the out-of-plane bending vibration peak groups of C-H.

[0058] Example 1

[0059] This example is to illustrate the ultraviolet curable adhesive system prepared by the present invention.

[0060] Use 77 parts by weight of acrylate functional monomers (containing 30 parts by weight of trimethylolpropane triacrylate, 15 parts by weight of pentaerythritol triacrylate, 15 parts by weight of trimethylolpropane trimethacrylate, 15 parts by weight of methoxypolyethylene glycol monoacrylate), 3 parts by weight of photoinitiator (1 part by weight of benzoin methyl ether, 1 part by weight of dimethoxyacetophenone, 1 part by weight of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-propan-1-one), 17 parts by weight of prepolymer 1 prepared in Preparation Example 1, 1 part by weight of antioxidant hindered phenol, 1 part by weight of adhesion promoter KH-570, and 1 part by weight of co-initiator N,N-dimethylaminoethyl methacrylate. Mix them under a vacuum of -0.05 MPa and stir mechanically at a speed of 900 revolutions per minute in the dark for 3 hours until homogeneous to obtain an ultraviolet-curable adhesive system.

[0061] Example 2

[0062] This example is to illustrate the ultraviolet-curable adhesive system prepared by the present invention.

[0063] Use 65 parts by weight of acrylate functional monomers (containing 46 parts by weight of trimethylolpropane triacrylate, 8 parts by weight of pentaerythritol triacrylate, 6 parts by weight of trimethylolpropane trimethacrylate, 5 parts by weight of methoxypolyethylene glycol monoacrylate), 5 parts by weight of photoinitiator (1 part by weight of benzoin ethyl ether, 1 part by weight of diethoxyacetophenone, 1 part by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1 part by weight of hydroxycyclohexyl phenyl ketone, 1 part by weight of 2-hydroxy-2-methylpropiophenone), 25 parts by weight of prepolymer 2 prepared in Preparation Example 2, 2 parts by weight of antioxidant p-benzoquinone, 1 part by weight of adhesion promoter KH-560, and 2 parts by weight of co-initiator N,N-dimethylaminoethyl methacrylate (containing 1 part by weight of N,N-dimethylaminoethyl methacrylate and 1 part by weight of p-dimethylaminobenzoate). Mix them under a vacuum of -0.05 MPa and stir mechanically at a speed of 900 revolutions per minute in the dark for 3 hours until homogeneous to obtain an ultraviolet-curable adhesive system.

[0064] Example 3

[0065] This example is to illustrate the ultraviolet-curable adhesive system prepared by the present invention.

[0066] 70 parts by weight of acrylate functional monomers are used (including 16 parts by weight of trimethylolpropane trimethacrylate, 18 parts by weight of methoxymonoacrylate of hexanediol, 26 parts by weight of methoxymonoacrylate of glycerol, 10 parts by weight of ethoxylated trimethylol dimethacrylate), 2 parts by weight of photoinitiators (0.5 part by weight of n-butyl benzoate, 0.5 part by weight of dimethoxy phenyl acetophenone, 0.5 part by weight of hydroxy dimethyl acetophenone, 0.5 part by weight of trimethylbenzoyl-ethoxy-phenyl phosphine oxide), 25 parts by weight of prepolymer 3 prepared in Preparation Example 3, 1 part by weight of antioxidant p-benzoquinone, 1 part by weight of adhesion promoter KH-570, and 1 part by weight of co-initiator p-dimethylaminobenzoate are mixed. Under a vacuum of -0.05 MPa, mechanical stirring is carried out at a rotation speed of 900 revolutions per minute in the dark for 3 hours until uniform, and an ultraviolet curable adhesive system is obtained.

[0067] Example 4

[0068] This example is to illustrate the ultraviolet curable adhesive system prepared by the present invention.

[0069] 65 parts by weight of acrylate functional monomers are used (including 20 parts by weight of methoxymonoacrylate of hexanediol, 20 parts by weight of methoxymonoacrylate of glycerol, 18 parts by weight of ethoxylated trimethylol dimethacrylate, 7 parts by weight of methoxymonoacrylate of ethoxylated neopentyl glycol), 4 parts by weight of photoinitiators (1 part by weight of hydroxycyclohexyl phenyl ketone, 1 part by weight of diethoxy acetophenone, 1 part by weight of trimethylbenzoyl-diphenyl phosphine oxide, 1 part by weight of bis(trimethylbenzoyl)phenyl phosphine oxide), 28 parts by weight of prepolymer 4 prepared in Preparation Example 4, 1 part by weight of antioxidant p-benzoquinone, 1 part by weight of adhesion promoter KH-560, and 1 part by weight of co-initiator (including 0.5 part by weight of N,N-dimethylaminomethyl acrylate and 0.5 part by weight of p-dimethylaminobenzoate) are mixed. Under a vacuum of -0.05 MPa, mechanical stirring is carried out at a rotation speed of 900 revolutions per minute in the dark for 3 hours until uniform, and an ultraviolet curable adhesive system is obtained.

[0070] Example 5

[0071] This example is to illustrate the ultraviolet curable adhesive system prepared by the present invention.

[0072] The UV-curable adhesive system was prepared in the same manner as in Example 1, except that: 75 parts by weight of acrylate functional monomers were used (including 20 parts by weight of trimethylolpropane triacrylate, 20 parts by weight of glycerol monomethacrylate, 18 parts by weight of trimethylolpropane triacrylate, 17 parts by weight of glycerol monomethacrylate), 1 part by weight of photoinitiator (0.3 parts by weight of dimethoxyacetophenone, 0.3 parts by weight of diethoxyacetophenone, 0.4 parts by weight of trimethylbenzoyl-diphenylphosphine oxide), 22 parts by weight of prepolymer 1 prepared in Preparation Example 1, 0.5 parts by weight of antioxidant p-benzoquinone, 0.5 parts by weight of adhesion promoter KH-560, 1 part by weight of co-initiator (including 0.5 parts by weight of N,N-dimethylaminomethyl acrylate and 0.5 parts by weight of p-dimethylaminobenzoate), and the same preparation method as in Example 1 was used.

[0073] Example 6

[0074] This example is to illustrate the UV-curable adhesive system prepared by the present invention.

[0075] The UV-curable adhesive system was prepared in the same manner as in Example 1, except that: 80 parts by weight of acrylate functional monomers were used (including 20 parts by weight of ethoxylated neopentyl glycol monomethacrylate, 20 parts by weight of glycerol monomethacrylate, 20 parts by weight of ethoxylated neopentyl glycol monomethacrylate, 20 parts by weight of pentaerythritol triacrylate), 1 part by weight of photoinitiator (0.25 parts by weight of benzoin ethyl ether, 0.25 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 0.25 parts by weight of hydroxydimethylacetophenone, 0.25 parts by weight of bis(trimethylbenzoyl)phenylphosphine oxide), 17 parts by weight of prepolymer 2 prepared in Preparation Example 2, 0.5 parts by weight of antioxidant p-benzoquinone, 0.5 parts by weight of adhesion promoter KH-560, 1 part by weight of co-initiator (including 0.5 parts by weight of N,N-dimethylaminomethyl acrylate and 0.5 parts by weight of p-dimethylaminobenzoate), and the same preparation method as in Example 1 was used.

[0076] Example 7

[0077] This example is to illustrate the UV-curable adhesive system prepared by the present invention.

[0078] The UV-curable adhesive system was prepared in the same manner as in Example 1, except that: 60 parts by weight of acrylate functional monomers were used (including 15 parts by weight of triol methoxy monoacrylate, 15 parts by weight of pentaerythritol triacrylate, 10 parts by weight of hexanediol methoxy monoacrylate, 20 parts by weight of ethoxylated neopentyl glycol methoxy monoacrylate), 3 parts by weight of photoinitiator (1 part by weight of benzoin n-butyl ether, 1 part by weight of dimethoxy phenyl acetophenone, 1 part by weight of trimethylbenzoyl-ethoxy-phenyl phosphine oxide), 30 parts by weight of prepolymer 4 prepared in Preparation Example 4, 2 parts by weight of antioxidant p-benzoquinone, 2 parts by weight of adhesion promoter KH-560, 3 parts by weight of co-initiator (including 1.5 parts by weight of N,N-dimethylaminomethyl acrylate and 1.5 parts by weight of p-dimethylaminobenzoate), and the same preparation method as in Example 1 was used.

[0079] Comparative Example 1

[0080] The UV-curable adhesive system was prepared in the same manner as in Example 1, except that: prepolymer 1 prepared in Preparation Example 1 was not contained, and the same preparation method as in Example 1 was used.

[0081] Comparative Example 2

[0082] The UV-curable adhesive system was prepared in the same manner as in Example 1, except that: the acrylate functional monomer formulation was different, specifically 77 parts by weight of ethyl acrylate functional monomer, and the same preparation method as in Example 1 was used.

[0083] Comparative Example 3

[0084] The UV-curable adhesive system was prepared in the same manner as in Example 2, except that: the acrylate functional monomer formulation was different, it was only a single acrylate functional monomer, specifically 25 parts by weight of 2-hydroxyethyl acrylate, and the same preparation method as in Example 1 was used.

[0085] Comparative Example 4

[0086] The UV-curable adhesive system was prepared in the same manner as in Example 3, except that: the contents of each component were different, specifically 20 parts by weight of acrylate functional monomers were used (including 5 parts by weight of trimethylolpropane trimethacrylate, 5 parts by weight of hexanediol methoxy monoacrylate, 5 parts by weight of glycerol methoxy monoacrylate, 5 parts by weight of ethoxylated trimethylol diacrylate), 20 parts by weight of photoinitiator, 20 parts by weight of prepolymer 3 prepared in Preparation Example 3, 10 parts by weight of antioxidant p-benzoquinone, 10 parts by weight of adhesion promoter KH-570, 20 parts by weight of co-initiator p-dimethylaminobenzoate, and the same preparation method as in Example 1 was used.

[0087] Comparative Example 5

[0088] The UV-curable adhesive system was prepared in the same manner as in Example 4, except that the content of prepolymer 4 prepared in Preparation Example 4 was 10 parts by weight, and the same preparation method as in Example 1 was used.

[0089] Comparative Example 6

[0090] The UV-curable adhesive system was prepared in the same manner as in Example 1, except that "prepolymer 1 prepared in Preparation Example 1" was replaced with "organosilicon-modified epoxy resin KR470 prepolymer", and the same preparation method as in Example 1 was used.

[0091] Test Example

[0092] Partial performance parameters of each example and comparative example are shown in Table 1.

[0093] Table 1

[0094]

[0095]

[0096] Remarks:

[0097] a Viscosity test method: Measured with a Brookfield-RVT type dial-type rotational viscometer at 25 °C and 20 rpm.

[0098] b Tensile modulus measurement method: Refer to the measurement method of ISO 527-3.

[0099] c Tensile adhesion strength test method: After UV curing for 30 seconds, bond with a 4# needle - polypropylene (untreated surface), and the test temperature is 25 °C.

[0100] As can be seen from the above table, the viscosities, tensile moduli, tensile adhesion strengths, and linear curing shrinkage rates of Examples 1 - 7 are different, which is mainly closely related to the acrylate functional monomer formula, prepolymer formula, and content; compared with Examples 1 - 7, in Comparative Examples 1 - 6, it can be seen that whether it is the tensile modulus or the tensile adhesion strength, the prepolymers prepared by the present invention are used in Examples 1 - 7, which improves the viscosity of the adhesive and has a better bonding effect on the needle. This is because the interpenetrating prepolymer itself has good toughness, and there are unreacted acrylate structures in the prepolymer. When irradiated with UV light, the unreacted acrylate structures can react with acrylate functional monomers again to form a crosslinked network structure, thus having higher strength and stability and achieving better effects.

[0101] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A UV-curable adhesive system for syringe needle bonding, characterized in that: The adhesive system includes the following components which are protected from light and stored separately: 60-80 parts by weight of acrylate functional monomer; 1-5 parts by weight of a photoinitiator; 15-30 parts by weight of a prepolymer, wherein the prepolymer comprises 45-55 parts by weight of an epoxy resin, 15-25 parts by weight of acrylic acid or methacrylic acid, and 35-45 parts by weight of triphenylphosphine, which are protected from light and stored separately; 1-5 parts by weight of other functional adjuvants.

2. The UV-curable adhesive system according to claim 1, wherein: The adhesive system includes the following components which are protected from light and stored separately: 65-77 parts by weight of acrylate functional monomer, 2-5 parts by weight of photoinitiator, 17-28 parts by weight of prepolymer, and 3-5 parts by weight of other functional auxiliary agents.

3. The UV-curable adhesive system according to claim 1 or 2, wherein: The preparation method of the prepolymer comprises: in the presence of triphenylphosphine, epoxy resin and acrylic acid or methacrylic acid are stirred at 100-110° C. for 4-5 hours under nitrogen protection and light-proof conditions, and then the prepolymer is obtained.

4. The UV-curable adhesive system according to claim 1 or 2, wherein: The epoxy resin includes a bisphenol A epoxy resin represented by formula (1) or an epoxy novolac resin represented by formula (2); Among them, n1 is 15-30; Among them, n is 15-30.

5. The UV-curable adhesive system according to claim 1 or 2, wherein: The acrylate is selected from at least two of trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, hexanediol methoxy monoacrylate, glycerol methoxy monoacrylate, ethoxylated trimethylol diacrylate, ethoxylated neopentyl glycol methoxy monoacrylate, trimethylolpropane triacrylate, methyl hydroxymethyl acrylate, hydroxyethyl acrylate, methyl hydroxyethyl acrylate and 2-hydroxyethyl acrylate; Preferably, the acrylate is selected from at least two of trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, hexanediol methoxy monoacrylate, glycerol methoxy monoacrylate, ethoxylated trimethylol diacrylate, ethoxylated neopentyl glycol methoxy monoacrylate and trimethylolpropane triacrylate.

6. The UV-curable adhesive system according to claim 1 or 2, wherein: The photoinitiator is selected from one or more of benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether, dimethoxyphenyl acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinebenzylphenyl)butanone, hydroxycycloethyl phenyl ketone, hydroxydimethylacetophenone, 2-hydroxy-2-methylphenylpropane-1-one, trimethylbenzoyl-ethoxy-phenylphosphine oxide, trimethylbenzoyl-diphenylphosphine oxide, bis(trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropiophenone and 2,2-dimethoxy-2-phenylacetophenone; Preferably, the photoinitiator is selected from one or more of benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether, dimethoxyphenyl acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinebenzylphenyl)butanone, hydroxycycloethyl phenyl ketone, hydroxydimethylacetophenone, 2-hydroxy-2-methylphenylpropane-1-one, trimethylbenzoyl-ethoxy-phenylphosphine oxide, trimethylbenzoyl-diphenylphosphine oxide and bis(trimethylbenzoyl)phenylphosphine oxide.

7. The UV-curable adhesive system according to claim 1 or 2, wherein: The other functional adjuvants include one or more of antioxidants, adhesion promoters and co-initiators; and / or, the antioxidant is hindered phenol and / or p-benzoquinone; and / or, the adhesion promoter is methacryloxypropyltrimethoxysilane and / or 2,3-glycidoxypropyltrimethoxysilane; And / or, the co-initiator is N,N-dimethylaminomethacrylate and / or p-dimethylaminobenzoate.

8. A method for preparing the UV-curable adhesive system according to any one of claims 1 to 7, characterized in that: The preparation method comprises: mixing acrylate functional monomers, photoinitiators, prepolymers and other functional auxiliary agents under light-proof conditions to obtain an ultraviolet light-curing adhesive system.

9. The preparation method according to claim 8, wherein: The mixing conditions include: vacuum degree of -0.1 MPa to -0.01 MPa, rotation speed of 800-1000 rpm, and light-proof stirring time of 2-3 hours.

10. Use of the UV-curable adhesive system according to any one of claims 1 to 7 as a sterile syringe needle glue in the production and preparation of disposable sterile syringe needles.

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