Dual-curing adhesive system for gluing syringe needle and preparation method and application of dual-curing adhesive system

By adopting a dual curing adhesive system, using components such as acrylic and/or acrylic acid and/or acrylic acid functional monomers, isocyanate functional monomers and interpenetrating network prepolymers, the problems of poor curing effect and insufficient bonding strength at the glue joints of medical syringes are solved, and the high-strength and rapid curing effect is achieved, which is suitable for the production of sterile syringes.

CN120020195APending Publication Date: 2025-05-20CHINA PETROLEUM & CHEMICAL CORP +1
View PDF 0 Cites 0 Cited by

Patent Information

Application Number
CN202311537265.0
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2023-11-17
Publication Date
2025-05-20

AI Technical Summary

Technical Problem

In use, existing UV light curing adhesives have problems such as limited UV penetration ability, poor curing effect, small cross-linking degree of prepolymer, insufficient cohesion strength, and insufficient bonding strength. It is especially difficult to achieve firm bonding at the glue joints of medical syringe needles.

Method used

A dual curing adhesive system is adopted, which includes acrylic and/or acrylate functional monomers, isocyanate functional monomers, photoinitiators, acrylic and/or acrylate prepolymers and other functional adjuvants that are stored away from light. Through specific component ratios and preparation methods, adhesives with interpenetrating network structure are formed, which improves their wetting effect and chemical bonding effects, thereby achieving rapid curing and increasing strength.

Benefits of technology

This dual-curing adhesive system has the characteristics of strong bonding power, fast curing and excellent mechanical properties. It can effectively improve the bonding strength and chemical resistance of medical syringe needles, and is suitable for the production and preparation of disposable sterile syringes.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure CN120020195A_ABST
    Figure CN120020195A_ABST
Patent Text Reader

Abstract

The invention relates to the technical field of adhesives, and discloses a dual-curing adhesive system for gluing syringe needles and a preparation method and application of the dual-curing adhesive system for gluing syringe needles, and the adhesive system comprises the following components which are lucifugal and independently preserved: 40-80 parts by weight of acrylic acid and / or acrylate functional monomer; 1-3 parts by weight of an isocyanate functional monomer; 2-4 parts by weight of a photoinitiator; 15-30 parts by weight of an acrylic acid and / or acrylate prepolymer; the prepolymer comprises 96-98 parts by weight of acrylic acid and / or acrylate functional monomer and 2-4 parts by weight of photoinitiator which are kept away from light and are respectively and independently stored; and 1-3 parts by weight of other functional auxiliary agents. The dual-curing adhesive system has the characteristics of strong bonding force, fast curing and excellent mechanical properties.
Need to check novelty before this filing date? Find Prior Art

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and in particular, to a dual-curing adhesive system for bonding syringe needles, a preparation method thereof, and an application thereof. Background Art

[0002] UV 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 curing is a new, efficient, energy-saving and environmentally friendly 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 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 and 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 prefilled syringes currently are a new type of drug packaging form composed of a hollow syringe barrel (which can be equipped with a pre-connected needle), a rubber piston, a needle cap or a cone cap, and a push rod. Among them, due to the characteristics of high polymerization efficiency, short time, low cost, and non-toxicity of UV radiation, the syringe barrel and the needle are generally bonded together by a UV-curing adhesive. However, some problems have also emerged in the use of UV curing. First, the penetration ability of ultraviolet light is limited, and for relatively thick syringe barrels and needles, the curing effect of ultraviolet light is not good; second, acrylate, an important material of UV-curing adhesives, has poor wettability on the metal surface, and there will be a problem of insufficient bonding strength when acrylate adhesives are used on metals. Summary of the Invention

[0004] The object of the present invention is to overcome the defects of the prior art, such as the limited penetration ability of ultraviolet light, poor curing effect, small crosslinking degree of prepolymers, insufficient cohesive strength, and insufficient bonding strength, and to provide a dual-curing adhesive system for bonding syringe needles, a preparation method thereof, and an application thereof. The dual-curing adhesive system has the characteristics of "strong bonding force", "fast curing", and "excellent mechanical properties".

[0005] To achieve the above object, in the first aspect of the present invention, there is provided a dual-curing adhesive system for bonding syringe needles, wherein the adhesive system includes the following components that are stored separately and protected from light:

[0006] 40 - 80 parts by weight of acrylic acid and / or acrylate functional monomers;

[0007] 1 - 3 parts by weight of isocyanate functional monomers;

[0008] 2 - 4 parts by weight of photoinitiators;

[0009] 15 - 30 parts by weight of acrylic acid and / or acrylate prepolymers; the prepolymers include 96 - 98 parts by weight of acrylic acid and / or acrylate functional monomers and 2 - 4 parts by weight of photoinitiators that are stored away from light;

[0010] 1 - 3 parts by weight of other functional adjuvants.

[0011] In a second aspect of the present invention, there is provided a method for preparing the aforementioned dual - curing adhesive system, wherein the preparation method includes:

[0012] (1) Contact and dissolve acrylic acid and / or acrylate functional monomers, isocyanate functional monomers, acrylic acid and / or acrylate prepolymers, and other functional adjuvants to obtain a mixture;

[0013] (2) Mix the mixture with photoinitiators to obtain a dual - curing adhesive system.

[0014] In a third aspect of the present invention, there is provided an application of the aforementioned dual - curing adhesive system as a needle glue for a sterile syringe in the production and preparation of disposable sterile syringe needles.

[0015] Through the above - mentioned technical solutions, for the requirements of firmly bonding medical needles, such as disposable sterile syringes, the dual - curing adhesive system of the present invention has the characteristics of convenient operation, firm bonding, and good chemical resistance. Description of the Drawings

[0016] Figure 1 is the infrared spectrum of prepolymer 1 prepared in Preparation Example 1 of the present invention;

[0017] Figure 2 is the infrared spectrum of prepolymer 2 prepared in Preparation Example 2 of the present invention. Detailed Description of the Invention

[0018] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. 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.

[0019] As described above, the first aspect of the present invention provides a dual-curing adhesive system for syringe needle bonding, wherein the adhesive system includes the following components that are protected from light and stored independently:

[0020] 40 - 80 parts by weight of acrylic acid and / or acrylate functional monomers;

[0021] 1 - 3 parts by weight of isocyanate functional monomers;

[0022] 2 - 4 parts by weight of photoinitiators;

[0023] 15 - 30 parts by weight of acrylic acid and / or acrylate prepolymers; the prepolymers include 96 - 98 parts by weight of acrylic acid and / or acrylate functional monomers and 2 - 4 parts by weight of photoinitiators that are protected from light;

[0024] 1 - 3 parts by weight of other functional auxiliaries.

[0025] The inventors of the present invention have found that: in the present invention, by utilizing the characteristics of convenient operation, firm adhesion, and good chemical resistance of acrylic acid and / or acrylate functional monomers and isocyanate functional monomers, prepolymers with an interpenetrating network structure are introduced into the system, greatly strengthening the wetting effect and chemical bond action of the adhesive, achieving the effects of rapid curing and increased strength, effectively improving the performance of the cured product and the usage efficiency of the adhesive. In addition, by adding isocyanate functional monomers, the relative slippage between polymer chains is effectively restricted, and the cohesive strength and thermal stability of the crosslinked structure are improved. After curing, it has high adhesive strength, small volume shrinkage, excellent heat resistance and solvent resistance, and can be used as a needle glue for sterile syringes.

[0026] According to the present invention, preferably, the adhesive system includes the following components that are protected from light:

[0027] 63 - 70 parts by weight of acrylic acid and / or acrylate functional monomers, 1 - 3 parts by weight of isocyanate functional monomers, 2 - 4 parts by weight of photoinitiators, 24 - 28 parts by weight of acrylic acid and / or acrylate prepolymers, 1 - 3 parts by weight of other functional auxiliaries.

[0028] According to the present invention, the preparation method of the prepolymer includes: stirring acrylic acid and / or acrylate functional monomers and photoinitiators at room temperature for 5 - 10 minutes under nitrogen protection to obtain a mixture, and then discharging the mixture after irradiating it with ultraviolet light for 30 - 60 seconds.

[0029] In the present invention, the prepolymer is an interpenetrating network prepolymer.

[0030] According to the present invention, the isocyanate functional monomer is selected from one or more of trifunctional isocyanate KL-1202, toluene-3,5-diisocyanate, and diphenylmethane diisocyanate.

[0031] In the present invention, the trifunctional isocyanate KL-1202 has the structure shown in formula (1), toluene-3,5-diisocyanate has the structure shown in formula (2), and diphenylmethane diisocyanate has the structure shown in formula (3):

[0032]

[0033] According to the present invention, the acrylic acid and / or acrylate functional monomer is selected from at least two of trimethylolpropane triacrylate, methylol methacrylate, hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, tert-butyl acrylate, acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, methoxypentaerythritol acrylate, methoxypentaerythritol acrylate, ethoxylated trimethylolpropane diacrylate, ethoxylated neopentyl glycol monomethacrylate, and isooctyl methacrylate.

[0034] According to the present invention, preferably, the acrylic acid and / or acrylate functional monomer is selected from at least two of trimethylolpropane triacrylate, methylol methacrylate, hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, tert-butyl acrylate, acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, and isooctyl methacrylate.

[0035] According to the present invention, the photoinitiator is selected from one or more of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, 2,2-dimethoxy-2-phenylacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether, dimethoxyphenylacetophenone, diethoxyphenylacetophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone, 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-propanone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, hydroxycyclohexyl phenyl ketone, hydroxydimethyl phenylacetone, 2-hydroxy-2-methylphenylpropan-1-one, trimethylbenzoyl-ethoxy-phenylphosphine oxide, trimethylbenzoyl-diphenylphosphine oxide, and bis(trimethylbenzoyl)phenylphosphine oxide.

[0036] According to the present invention, preferably, the photoinitiator is selected from one or more of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, 2,2-dimethoxy-2-phenylacetophenone, benzoin methyl ether, benzoin ethyl ether, and benzoin n-butyl ether.

[0037] According to the present invention, the other functional adjuvants include antioxidants and / or co-initiators.

[0038] According to the present invention, the antioxidant is a hindered phenol and / or p-benzoquinone.

[0039] According to the present invention, the co-initiator is N,N-dimethylaminomethyl acrylate and / or p-dimethylaminobenzoate.

[0040] The second aspect of the present invention provides a method for preparing the aforementioned dual-curing adhesive system, wherein the preparation method includes:

[0041] (1) Contacting and dissolving acrylic acid and / or acrylate functional monomers, isocyanate functional monomers, acrylic acid and / or acrylate prepolymers, and other functional adjuvants to obtain a mixture;

[0042] (2) Mixing the mixture with a photoinitiator to obtain a dual-curing adhesive system.

[0043] According to the present invention, in step (2), the conditions for mixing include: stirring at room temperature in the dark for 1-2 hours under a vacuum of -0.1 MPa to -0.01 MPa and a rotation speed of 800-1000 revolutions per minute.

[0044] The third aspect of the present invention provides an application of the aforementioned dual-curing adhesive system as a needle glue for a sterile syringe in the production and preparation of disposable sterile syringe needles.

[0045] The present invention will be described in detail below through examples.

[0046] In the following examples and comparative examples:

[0047] The viscosity parameter was measured by the method of GB / T 2794-1995;

[0048] The tensile modulus and tensile adhesion strength parameters were measured by the method of GB / T 7124-2008;

[0049] The linear curing shrinkage rate was measured by a displacement experiment.

[0050] All kinds of monomers and their synthetic reagents were purchased from InnoChem Co., Ltd.

[0051] The room temperature refers to 25 °C.

[0052] Preparation Example 1

[0053] 97 parts by weight of acrylate monomers (33 parts by weight of trimethylolpropane triacrylate, 30 parts by weight of methylol methacrylate, 34 parts by weight of hydroxyethyl acrylate) and 3 parts by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide were stirred at room temperature for 5 minutes under nitrogen protection, and then the mixture was irradiated with ultraviolet light for 60 seconds to obtain a colorless viscous liquid prepolymer 1.

[0054] Among them, Figure 1 is the infrared spectrum of prepolymer 1. Figure 1 In it, the stretching vibration peak of -OH is at 3200 - 3500 cm -1 ; the stretching vibration peaks of -CH -1 and -CH 3 are at 2950 and 2860 cm 2 respectively; the absorption peak appearing at 1725 cm -1 is the stretching vibration peak of the ester group; the absorption peak appearing at 1600 - 1650 cm -1 represents the characteristic peak of C=C; the bending vibration peaks of the alkyl group (-CH -1 ) are at 1450 and 1410 cm 3 ; the absorption peak appearing at 1260 cm -1 represents the in-plane deformation vibration of -OH; the absorption peaks at 1160 cm -1 and 1070 cm -1 correspond to the stretching vibrations of C-C-C and C-O respectively. The peaks at 1450 and 1410 may also be the characteristic peaks of ketones.

[0055] Preparation Example 2

[0056] 96 parts by weight of acrylate monomers (25 parts by weight of tert-butyl acrylate, 33 parts by weight of 2-hydroxyethyl methacrylate, 38 parts by weight of isooctyl methacrylate) and 4 parts by weight of 2-hydroxy-2-methyl-1-phenylpropanone were stirred at room temperature for 5 minutes under nitrogen protection, and then the mixture was irradiated with ultraviolet light for 60 seconds to obtain a colorless viscous liquid prepolymer 2.

[0057] Among them, Figure 2 is the infrared spectrum of prepolymer 2. Figure 2 In it, the stretching vibration peak of -OH is at 3240 - 3550 cm -1 ; the stretching vibration peaks of -CH -1 and -CH 3 are at 2960 and 2880 cm 2 respectively; the absorption peak at 1730 cm -1The absorption peak appearing at [the specific position] is the stretching vibration peak of the ester group; the peaks at 1460 and 1395 cm -1 are the bending vibration peaks of the alkyl group; the peak at 1247 cm -1 The absorption peak appearing at [the specific position] represents the in-plane deformation vibration of -OH; at 1000 cm -1 and 1200 cm -1 The absorption peaks between correspond to the stretching vibrations of C-C-C and C-O-C; the peaks at 800 - 900 cm -1 are the out-of-plane bending vibration peak groups of C-H. The peaks at 1460 and 1395 may also be the characteristic peaks of the ketone.

[0058] Preparation Example 3

[0059] 98 parts by weight of acrylate monomers (30 parts by weight of 2-hydroxyethyl methacrylate, 35 parts by weight of methylol methacrylate, 33 parts by weight of 2-hydroxyethyl acrylate) and 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide were stirred at room temperature for 5 minutes under nitrogen protection, and then the mixture was irradiated with ultraviolet light for 60 seconds to obtain a colorless viscous liquid prepolymer 2.

[0060] Preparation Example 4

[0061] 98 parts by weight of acrylate monomers (28 parts by weight of 2-hydroxyethyl acrylate, 35 parts by weight of tert-butyl acrylate, 35 parts by weight of acrylic acid) and 2 parts by weight of 2,2-dimethoxy-2-phenylacetophenone were stirred at room temperature for 5 minutes under nitrogen protection, and then the mixture was irradiated with ultraviolet light for 60 seconds to obtain a colorless viscous liquid prepolymer 4.

[0062] Example 1

[0063] This example is to illustrate the dual-curing adhesive system prepared by the present invention.

[0064] 3 parts by weight of isocyanate functional monomers (1 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 1 part by weight of toluene-3,5-diisocyanate shown in formula (2), 1 part by weight of diphenylmethane diisocyanate shown in formula (3)), 65 parts by weight of acrylic(ester) functional monomers (25 parts by weight of trimethylolpropane triacrylate, 15 parts by weight of 2-hydroxyethyl acrylate, 25 parts by weight of tert-butyl acrylate), 3 parts by weight of photoinitiators (1 part by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1 part by weight of 2-hydroxy-2-methyl-1-phenylpropanone, 1 part by weight of 2,2-dimethoxy-2-phenylacetophenone), 27 parts by weight of prepolymer 1 prepared in Preparation Example 1, 1 part by weight of antioxidant hindered phenol, and 1 part by weight of co-initiator N,N-dimethylaminomethyl acrylate were mixed. Under a vacuum of -0.05 MPa and a rotation speed of 900 rpm, it was mechanically stirred in the dark for 1.5 hours until uniform to obtain a dual-curing adhesive system.

[0065] Example 2

[0066] This example is to illustrate the dual-curing adhesive system prepared by the present invention.

[0067] Mix 1.5 parts by weight of isocyanate functional monomers (0.5 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 0.5 part by weight of toluene-3,5-diisocyanate shown in formula (2), 0.5 part by weight of diphenylmethane diisocyanate shown in formula (3)), 69 parts by weight of acrylic (ester) functional monomers (25 parts by weight of methyl methacrylate hydroxymethyl, 24 parts by weight of hydroxyethyl methacrylate, 20 parts by weight of acrylic acid), 2.5 parts by weight of photoinitiators (1 part by weight of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1.5 parts by weight of 2-hydroxy-2-methyl-1-phenylpropanone), 25 parts by weight of prepolymer 2 prepared in Preparation Example 2, 1 part by weight of antioxidant hindered phenol, and 1 part by weight of co-initiator N,N-dimethylaminomethyl acrylate. Under a vacuum of -0.05 MPa, stir mechanically in the dark at a speed of 900 revolutions per minute for 1.5 hours until uniform to obtain a dual-curing adhesive system.

[0068] Example 3

[0069] This example is to illustrate the dual-curing adhesive system prepared by the present invention.

[0070] Mix 2 parts by weight of isocyanate functional monomers (1 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 0.5 part by weight of toluene-3,5-diisocyanate shown in formula (2), 0.5 part by weight of diphenylmethane diisocyanate shown in formula (3)), 63 parts by weight of acrylic (ester) functional monomers (22 parts by weight of hydroxyethyl acrylate, 18 parts by weight of hydroxyethyl methacrylate, 23 parts by weight of 2-hydroxyethyl acrylate), 4 parts by weight of photoinitiators (2 parts by weight of (2,4,6-trimethylbenzoyl)phosphine oxide, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), 28 parts by weight of prepolymer 3 prepared in Preparation Example 3, 1.5 parts by weight of antioxidant hindered phenol, and 1.5 parts by weight of co-initiator N,N-dimethylaminomethyl acrylate. Under a vacuum of -0.05 MPa, stir mechanically in the dark at a speed of 900 revolutions per minute for 1.5 hours until uniform.

[0071] Example 4

[0072] This example is to illustrate the dual-curing adhesive system prepared by the present invention.

[0073] Mix 1 part by weight of isocyanate functional monomers (0.5 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 0.3 part by weight of toluene-3,5-diisocyanate shown in formula (2), 0.2 part by weight of diphenylmethane diisocyanate shown in formula (3)), 70 parts by weight of acrylic (ester) functional monomers (22 parts by weight of trimethylolpropane triacrylate, 25 parts by weight of 2-hydroxyethyl methacrylate, 23 parts by weight of tert-butyl acrylate), 2 parts by weight of photoinitiators (1 part by weight of 2-hydroxy-2-methyl-1-phenylpropanone, 1 part by weight of 2,2-dimethoxy-2-phenylacetophenone), 24 parts by weight of prepolymer 4 prepared in Preparation Example 4, 1 part by weight of antioxidant hindered phenol, and 2 parts by weight of co-initiator N,N-dimethylaminomethyl acrylate. Under a vacuum of -0.05 MPa and a rotation speed of 900 rpm, stir mechanically in the dark for 1.5 hours until homogeneous to obtain a dual-curing adhesive system.

[0074] Example 5

[0075] This example is to illustrate the dual-curing adhesive system prepared by the present invention.

[0076] Prepare a dual-curing adhesive system according to the same method as in Example 1, except that: mix 1.2 parts by weight of isocyanate functional monomers (0.4 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 0.4 part by weight of toluene-3,5-diisocyanate shown in formula (2), 0.4 part by weight of diphenylmethane diisocyanate shown in formula (3)), 70 parts by weight of acrylic (ester) functional monomers (17 parts by weight of trimethylolpropane triacrylate, 17 parts by weight of pentaerythritol triacrylate, 18 parts by weight of tert-butyl acrylate, 18 parts by weight of 2-hydroxyethyl methacrylate), 1.8 parts by weight of photoinitiators (0.6 part by weight of benzoin methyl ether, 0.6 part by weight of benzoin ethyl ether, 0.6 part by weight of benzoin n-butyl ether), 25 parts by weight of prepolymer 1 prepared in Preparation Example 1, 1 part by weight of antioxidant p-benzoquinone, and 1 part by weight of co-initiator p-dimethylaminobenzoate, and use the same preparation method as in Example 1.

[0077] Example 6

[0078] This example is to illustrate the dual-curing adhesive system prepared by the present invention.

[0079] A dual-curing adhesive system was prepared in the same manner as in Example 1, except that: 1 part by weight of isocyanate-functional monomers (0.3 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 0.4 part by weight of toluene-3,5-diisocyanate shown in formula (2), 0.3 part by weight of diphenylmethane diisocyanate shown in formula (3)), 70 parts by weight of acrylic (ester)-functional monomers (15 parts by weight of methyl methacrylate, 15 parts by weight of trimethylolpropane triacrylate, 20 parts by weight of hydroxyethyl acrylate, 20 parts by weight of pentaerythritol triacrylate), 2 parts by weight of photoinitiators (0.5 part by weight of benzoin methyl ether, 0.5 part by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 0.5 part by weight of 2-hydroxy-2-methyl-1-phenylpropanone, 0.5 part by weight of benzoin n-butyl ether), 25 parts by weight of prepolymer 2 prepared in Preparation Example 2, 1 part by weight of antioxidant p-benzoquinone, and 1 part by weight of co-initiator p-dimethylaminobenzoate were mixed using the same preparation method as in Example 1.

[0080] Example 7

[0081] This example is to illustrate the dual-curing adhesive system prepared by the present invention.

[0082] A dual-curing adhesive system was prepared in the same manner as in Example 1, except that: 1.5 parts by weight of isocyanate-functional monomers (0.5 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 0.5 part by weight of toluene-3,5-diisocyanate shown in formula (2), 0.5 part by weight of diphenylmethane diisocyanate shown in formula (3)), 66 parts by weight of acrylic (ester)-functional monomers (15 parts by weight of trimethylolpropane triacrylate, 15 parts by weight of hydroxyethyl acrylate, 16 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of acrylic acid), 2 parts by weight of photoinitiators (0.5 part by weight of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.5 part by weight of 2,2-dimethoxy-2-phenylacetophenone, 0.5 part by weight of benzoin ethyl ether, 0.5 part by weight of benzoin n-butyl ether), 28.5 parts by weight of prepolymer 3 prepared in Preparation Example 3, 1 part by weight of antioxidant p-benzoquinone, and 1 part by weight of co-initiator p-dimethylaminobenzoate were mixed using the same preparation method as in Example 1.

[0083] Comparative Example 1

[0084] A dual-curing adhesive system was prepared in the same manner as in Example 1, except that: it did not contain isocyanate-functional monomers and was prepared using the same method as in Example 1.

[0085] Comparative Example 2

[0086] The dual-curing adhesive system was prepared in the same manner as in Example 1, except that: it did not contain acrylic acid and / or acrylate functional monomers, and the same preparation method as in Example 1 was used.

[0087] Comparative Example 3

[0088] The dual-curing adhesive system was prepared in the same manner as in Example 2, except that: the acrylate functional monomer formulation was different, and it was only a single acrylate functional monomer, specifically: 1.5 parts by weight of isocyanate functional monomer (0.5 part by weight of trifunctional isocyanate KL-1202 shown in formula (1), 0.5 part by weight of toluene-3,5-diisocyanate shown in formula (2), 0.5 part by weight of diphenylmethane diisocyanate shown in formula (3)), 69 parts by weight of methyl methacrylate, 2.5 parts by weight of photoinitiator (1 part by weight of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1.5 parts by weight of 2-hydroxy-2-methyl-1-phenylpropanone), 25 parts by weight of prepolymer 2 prepared in Preparation Example 2, 1 part by weight of antioxidant hindered phenol, 1 part by weight of co-initiator N,N-dimethylaminomethyl acrylate, and the same preparation method as in Example 1 was used.

[0089] Comparative Example 4

[0090] The dual-curing adhesive system was prepared in the same manner as in Example 3, except that: the contents of each component were different, specifically:

[0091] 20 parts by weight of acrylic (ester) functional monomer (5 parts by weight of tert-butyl acrylate, 5 parts by weight of ethoxylated trimethylol diacrylate, 5 parts by weight of trimethylolpropane triacrylate, 5 parts by weight of hexanediol monomethacrylate), 10 parts by weight of prepolymer 4 prepared in Preparation Example 4, 65 parts by weight of isocyanate functional monomer (20 parts by weight of trifunctional isocyanate KL-1202 shown in formula (1), 20 parts by weight of toluene-3,5-diisocyanate shown in formula (2), 25 parts by weight of diphenylmethane diisocyanate shown in formula (3)), 2 parts by weight of photoinitiator (0.5 part by weight of dimethoxyphenylacetophenone, 0.5 part by weight of diethoxyphenylacetophenone, 0.5 part by weight of 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone, 0.5 part by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-propanone), 1.5 parts by weight of antioxidant hindered phenol, 1.5 parts by weight of co-initiator p-dimethylaminobenzoate, and the same preparation method as in Example 1 was used.

[0092] Comparative Example 5

[0093] The dual-curing 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.

[0094] Comparative Example 6

[0095] The dual-curing adhesive system was prepared in the same manner as in Example 1, except that: "prepolymer 1 prepared in Preparation Example 1" was replaced with "acrylonitrile-butadiene-styrene copolymer", and the same preparation method as in Example 1 was used.

[0096] Comparative Example 7

[0097] The dual-curing adhesive system was prepared in the same manner as in Example 1, except that: "isocyanate functional monomer" was replaced with "hexamethylene diisocyanate", and the same preparation method as in Example 1 was used.

[0098] Test Example

[0099] Partial performance parameters of each example and comparative example are shown in Table 1.

[0100] Table 1

[0101]

[0102]

[0103] Remarks:

[0104] a Viscosity test method: Measured with a Brookfield-RVT type dial-type rotational viscometer at 25 °C and 20 rpm.

[0105] b Tensile modulus measurement method: Refer to the measurement method of ISO 527-3.

[0106] c Tensile adhesion strength test method: After ultraviolet light curing for 30 seconds and heat curing at 80 °C for 10 minutes, bonding with a 4# needle - polypropylene (untreated surface), and the test temperature is 25 °C.

[0107] As can be seen from the above table, there are differences in the viscosity, tensile modulus, tensile adhesion strength, and linear curing shrinkage of Examples 1-7, which are mainly closely related to the isocyanate monomer formula, acrylic (ester) monomer formula, and the composition and content of the acrylic (ester) prepolymer; compared with Examples 1-7, in Comparative Examples 1-7, the adhesive using the dual-curing mechanism based on ultraviolet and heat of the present invention improves the adhesion strength and has a better adhesion effect on the needle. This is because the interpenetrating prepolymer itself has good toughness, and the crosslinked network structure formed by introducing the isocyanate crosslinking agent into the prepolymer has higher strength and stability.

[0108] 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 dual-cure adhesive system for gluing syringe needles, characterized in that: The adhesive system includes the following components which are protected from light and stored separately: 40-80 parts by weight of acrylic acid and / or acrylate functional monomers; 1-3 parts by weight of isocyanate functional monomer; 2-4 parts by weight of a photoinitiator; 15-30 parts by weight of acrylic acid and / or acrylic acid ester prepolymer; the prepolymer comprises 96-98 parts by weight of acrylic acid and / or acrylic acid ester functional monomers and 2-4 parts by weight of photoinitiator, which are protected from light and stored separately; 1-3 parts by weight of other functional adjuvants.

2. The dual cure adhesive system according to claim 1, wherein: The adhesive system includes the following components which are protected from light and stored separately: 63-70 parts by weight of acrylic acid and / or acrylic acid ester functional monomers, 1-3 parts by weight of isocyanate functional monomers, 2-4 parts by weight of photoinitiators, 24-28 parts by weight of acrylic acid and / or acrylic acid ester prepolymers, and 1-3 parts by weight of other functional auxiliary agents.

3. The dual-cure adhesive system according to claim 1 or 2, wherein: The preparation method of the prepolymer comprises: stirring acrylic acid and / or acrylate functional monomer and photoinitiator at room temperature for 5-10 minutes under nitrogen protection to obtain a mixture, and then irradiating the mixture with ultraviolet light for 30-60 seconds before discharging the mixture.

4. The dual-cure adhesive system according to claim 1 or 2, wherein: The isocyanate functional monomer is selected from one or more of trifunctional isocyanate KL-1202, toluene-3,5-diisocyanate and diphenylmethane diisocyanate.

5. The dual-cure adhesive system according to claim 1 or 2, wherein: The acrylic acid and / or acrylate functional monomer is selected from at least two of trimethylolpropane triacrylate, methyl hydroxymethylacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, tert-butyl acrylate, acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, hexanediol methoxy monoacrylate, glycerol methoxy monoacrylate, ethoxylated trimethylol diacrylate, ethoxylated neopentyl glycol methoxy monoacrylate and isooctyl methacrylate; Preferably, the acrylic acid and / or acrylate functional monomer is selected from at least two of trimethylolpropane triacrylate, methyl hydroxymethylacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, tert-butyl acrylate, acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate and isooctyl methacrylate.

6. The dual-cure adhesive system according to claim 1 or 2, wherein: The photoinitiator is selected from one or more of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl propiophenone, 2,2-dimethoxy-2-phenyl acetophenone, 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, hydroxydimethyl acetophenone, 2-hydroxy-2-methylphenylpropane-1-one, trimethylbenzoyl-ethoxy-phenyl phosphine oxide, trimethylbenzoyl-diphenyl phosphine oxide and bis (trimethylbenzoyl) phenyl phosphine oxide; Preferably, the photoinitiator is selected from one or more of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-propiophenone, 2,2-dimethoxy-2-phenylacetophenone, benzoin methyl ether, benzoin ethyl ether and benzoin n-butyl ether.

7. The dual-cure adhesive system according to claim 1 or 2, wherein: The other functional adjuvants include antioxidants and / or co-initiators; and / or, the antioxidant is hindered phenol and / or p-benzoquinone; And / or, the co-initiator is N,N-dimethylaminomethacrylate and / or p-dimethylaminobenzoate.

8. A method for preparing a dual-cure adhesive system according to any one of claims 1 to 7, characterized in that: The preparation method comprises: (1) contacting and dissolving acrylic acid and / or acrylic acid ester functional monomers, isocyanate functional monomers, acrylic acid and / or acrylic acid ester prepolymers and other functional auxiliary agents to obtain a mixture; (2) mixing the mixture with a photoinitiator to obtain a dual-cure adhesive system.

9. The method according to claim 8, wherein: In step (2), the mixing conditions include: vacuum degree of -0.1 MPa to -0.01 MPa, rotation speed of 800-1000 rpm, and stirring time of 1-2 hours at room temperature in the dark.

10. Use of the dual-curing 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.