CN111560233A - High-performance low-toxicity medical UV adhesive and preparation method thereof - Google Patents
High-performance low-toxicity medical UV adhesive and preparation method thereof Download PDFInfo
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- CN111560233A CN111560233A CN202010419599.8A CN202010419599A CN111560233A CN 111560233 A CN111560233 A CN 111560233A CN 202010419599 A CN202010419599 A CN 202010419599A CN 111560233 A CN111560233 A CN 111560233A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
A high-performance low-toxicity medical UV adhesive comprises the following components in parts by weight: 40-50 parts of polyurethane acrylate resin; 40-55 parts of low-molecular acrylate reactive diluent; 1-3 parts of an initiation accelerator; 1-10 parts of a coupling agent; 0.1-5 parts of a photoinitiator; wherein: the polyurethane acrylate is one or more of polyester polyurethane acrylate, polyether polyurethane acrylate, polybutadiene dimethacrylate and polycarbonate polyurethane acrylate resin, and is preferably polybutadiene dimethacrylate and carbonate polyurethane acrylate. The invention provides an environment-friendly ultraviolet curing adhesive product and a preparation method thereof, which are used for assembling and bonding medical consumables and have the advantages of low biotoxicity, low dissolution, low migration toxicity and low irritation.
Description
Technical Field
The invention belongs to the field of adhesives and preparation thereof, and particularly relates to a medical UV adhesive with high performance and low toxicity, and a preparation method of the adhesive.
Background
With the development of medical technology and the improvement of medical level in the world, various disposable or non-disposable medical consumables have been developed, which generally include needles, catheter assemblies, masks, protective clothing, breathing masks, liquid collection bags, blood collection and hemostasis devices, bandages for prosthesis, hearing aids, and the like. The consumables have the outstanding characteristics that different materials are needed for bonding, heavy load bearing is needed, the bonding surface is attractive, and quick assembly and bonding can be achieved instantly.
The adhesives used for assembling medical consumables in society are various, and the ultraviolet curing adhesive has high efficiency and low toxicity and environmental protection characteristics in the process and performance, so that the ultraviolet curing adhesive becomes a preferred assembling adhesive. The technology of the foreign ultraviolet curing adhesive is early started, products in the aspect of medical material ultraviolet curing adhesive are relatively mature, for example, disposable needle assembly bonding, catheter bonding, respirator bonding, laryngeal mask catheter bonding and the like are formed, and monopoly is formed in the application fields of contact lenses, light curing tooth repairing materials and the like. But less has been studied on the migratory toxicity or dissolution of the gel of the medical consumable assembly.
At present, the ultraviolet curing adhesive for medical instruments is researched late in China, and the research is focused on reducing the biotoxicity and the skin irritation of the product, improving the universality, the curing speed, the aging resistance and the like. Few documents intensively study on colloid migration toxicity or dissolubility, and related UV adhesives take N, N-dimethylacrylamide as a low-molecular acrylate active diluent, and have the defects of large smell, high residual monomer content, strong irritation and high toxicity.
Therefore, in view of the above current situations, the present application has made further studies on UV adhesives for medical use.
Disclosure of Invention
In view of the above disadvantages or shortcomings in the prior art, one of the objects of the present invention is to provide a medical UV adhesive with high performance and low toxicity, and the other object of the present invention is to provide a method for preparing the medical UV adhesive.
In order to solve the above technical problems, the present invention is solved by the following technical solutions.
The application relates to a high-performance low-toxicity medical UV adhesive which comprises the following components in parts by weight: 40-50 parts of polyurethane acrylate resin; 40-55 parts of low-molecular acrylate reactive diluent; 1-3 parts of an initiation accelerator; 1-10 parts of a coupling agent; 0.1-5 parts of a photoinitiator; wherein: the polyurethane acrylate is one or more of polyester polyurethane acrylate, polyether polyurethane acrylate, polybutadiene dimethacrylate and polycarbonate polyurethane acrylate resin, and is preferably polybutadiene dimethacrylate and carbonate polyurethane acrylate.
The low molecular acrylate reactive diluent is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, 2-phenoxyethyl acrylate, glycidyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, isobornyl acrylate, isobornyl methacrylate, phenoxyethyl methacrylate, dicyclopentanyl methacrylate, 1, 6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, propoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, dipentaerythritol tetraacrylate, morpholine acrylate and dimethylacrylamide; preferably hydroxyethyl methacrylate (good water resistance, low odor, better for use with polyester urethane acrylates), tripropylene glycol diacrylate (low odor, low irritation), tricyclodecane dimethanol diacrylate (fast reaction, low toxicity).
The organic amine promoter is preferably an active macromolecular organic amine promoter, and can well reduce biotoxicity.
Further, the photoinitiator is at least one of 184, 1108, 819, 1173, 379, 369, 907, ITX, 651, BP and one, and is preferably a macroinitiator one and a hydrogen-extracting initiator BP and CQ.
Further, the coupling agent is at least one of KH-550, KH-560, KH-570, Z-6032, Z-6300 and Z-6076, preferably KH-560 and KH-570.
The other medical high-performance low-toxicity UV adhesive comprises the following components in parts by weight: 40-50 parts of polycarbonate urethane acrylate resin with the molecular weight of 4000; 18-20 parts of hydroxyethyl methacrylate; 10-15 parts of isobornyl acrylate; 5-10 parts of tripropylene glycol diacrylate; 6-10 parts of tricyclo-sunflower alkyl dimethanol diacrylate; 2-3 parts of an organic amine accelerator; 0.5-1.5 parts of silane coupling agent; 1-3 parts of a photoinitiator; wherein: the photoinitiator is at least one of one, BP and CQ; the silane coupling agent is at least one of KH-550, KH-560 and KH-570.
The application relates to another high-performance low-toxicity medical UV adhesive which comprises the following components in parts by weight: 50 parts of polyester type polyurethane acrylate; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP 2 parts; and (5) 0.5 parts of one.
The other medical high-performance low-toxicity UV adhesive comprises the following components in parts by weight: 25 parts of polycarbonate urethane acrylate resin; polyester urethane acrylate 25; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 parts of (1); and (5) 0.5 parts of one.
The application relates to another high-performance low-toxicity medical UV adhesive which comprises the following components in parts by weight: 50 parts of polybutadiene dimethacrylate; 20 parts of hydroxybutyl methacrylate; 20 parts of propylene oxide neopentyl glycol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2.5 parts.
The preparation method of the high-performance low-toxicity medical UV adhesive comprises the following steps: s10: sequentially adding the polyurethane acrylate resin, the active acrylate monomer, the coupling agent and the photoinitiator into a stirring kettle according to the mass parts required by the formula, and stirring; s20: heating to 60 ℃ in the stirring process; s30: vacuumizing, keeping the vacuum degree to-0.095 MPa for 30 seconds, and continuously stirring for 2 hours; s40: and cooling to room temperature by using cooling water to prepare the adhesive.
Compared with the prior art, the invention has the following beneficial effects: the invention provides an environment-friendly ultraviolet curing adhesive product and a preparation method thereof, which are used for assembling and bonding medical consumables and have the advantages of low biotoxicity, low dissolution, low migration toxicity and low irritation.
Detailed Description
The present invention is described in further detail below by way of specific embodiments.
The following embodiments, in which the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout, are exemplary and are only for explaining the present invention, and are not to be construed as limiting the present invention.
The first embodiment is as follows:
the components and parts by weight selected in the first embodiment are as follows: 45 parts of polycarbonate urethane acrylate resin (molecular weight 4000); 20 parts of hydroxyethyl methacrylate; 13 parts of isobornyl acrylate; 7 parts of tripropylene glycol diacrylate; 9 parts of tricyclodecane dimethanol diacrylate; 2.5 parts of an organic amine accelerator; KH 570: 1 part; BP: 2 parts of (1); 0.5 part of one; CQ0.01 portion.
The preparation method comprises the following steps: according to the formula, 45 parts of polycarbonate urethane acrylate resin (with the molecular weight of 4000); 20 parts of hydroxyethyl methacrylate; 13 parts of isobornyl acrylate; 7 parts of tripropylene glycol diacrylate; 9 parts of tricyclodecane dimethanol diacrylate; 2.5 parts of an organic amine accelerator; KH 570: 1 part; BP: 2 parts of (1); 0.5 part of one; CQ0.01 portion. Adding into a stirring kettle, and stirring. During the stirring process, the temperature was raised to 60 ℃. After the temperature reaches 60 ℃, vacuumizing and stirring are carried out, the vacuum degree reaches-0.095 MPa for 30 seconds, and then stirring is continuously carried out for 2 hours. And finally, cooling the reaction kettle to room temperature by using cooling water to prepare the adhesive.
Example two:
the components and parts by weight selected in the second embodiment are as follows: 50 parts of polyester type polyurethane acrylate; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP 2 parts; and (5) 0.5 parts of one.
The preparation method comprises the following steps: according to the formula, 50 parts of polyester urethane acrylate; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP 2 parts; and (5) 0.5 parts of one. Adding into a stirring kettle, and stirring. During the stirring process, the temperature was raised to 60 ℃. After the temperature reaches 60 ℃, vacuumizing and stirring are carried out, the vacuum degree reaches-0.095 MPa for 30 seconds, and then stirring is continuously carried out for 2 hours. And finally, cooling the reaction kettle to room temperature by using cooling water to prepare the adhesive.
In the embodiment, the hydroxybutyl methacrylate has good water resistance, the toxicity of the tricyclodecane dimethanol diacrylate is low, and the tripropylene glycol diacrylate has the characteristics of low odor and low irritation, so that the product performance is better.
Example three:
the components and parts by weight selected in the third embodiment are as follows: 25 parts of polycarbonate urethane acrylate resin; polyester urethane acrylate 25; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 parts of (1); and (5) 0.5 parts of one.
The preparation method comprises the following steps: according to the formula, 25 parts of polycarbonate urethane acrylate resin; 25 parts of polyester type polyurethane acrylate; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 parts of (1); and (5) 0.5 parts of one. Adding into a stirring kettle, and stirring. During the stirring process, the temperature was raised to 60 ℃. After the temperature reaches 60 ℃, vacuumizing and stirring are carried out, the vacuum degree reaches-0.095 MPa for 30 seconds, and then stirring is continuously carried out for 2 hours. And finally, cooling the reaction kettle to room temperature by using cooling water to prepare the adhesive.
In the embodiment, the hydroxybutyl methacrylate has good water resistance, and the tripropylene glycol diacrylate has the characteristics of low odor and low irritation, so that the product performance is better.
Example four:
the components and parts by weight selected in the fourth example are as follows: 45 parts of polyester type polyurethane acrylate; 20 parts of tetrahydrofuran acrylate; 20 parts of dimethylacrylamide; 9 parts of acrylic morpholine; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 parts of (1); and (5) 0.5 parts of one.
The preparation method comprises the following steps: according to the formula, 45 parts of polyester urethane acrylate; 20 parts of tetrahydrofuran acrylate; 20 parts of dimethylacrylamide; 9 parts of acrylic morpholine; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 parts of (1); one0.5 part is added into a stirring kettle and stirred. During the stirring process, the temperature was raised to 60 ℃. After the temperature reaches 60 ℃, vacuumizing and stirring are carried out, the vacuum degree reaches-0.095 MPa for 30 seconds, and then stirring is continuously carried out for 2 hours. And finally, cooling the reaction kettle to room temperature by using cooling water to prepare the adhesive in the application.
In the embodiment, the tetrahydrofuran acrylate can be well used for plastic bonding, the bonding property is very good, but the sensitivity is strong, the toxicity is high, the dimethylacrylamide also has the defects of high toxicity and difficulty in controlling the amount of residual monomers, the acrylic morpholine has strong water solubility and is quick to dry, so that the product in the embodiment can be well used for bonding medical equipment which is not in contact with a human body.
Example five:
the components and parts by weight selected in the fifth embodiment are as follows: 40 parts of polyether urethane acrylate; 20 parts of hydroxybutyl methacrylate; 20 parts of tricyclodecane dimethanol diacrylate; 14 parts of acrylic morpholine; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2.5 parts.
The preparation method comprises the following steps: according to the formula, 40 parts of polyether urethane acrylate; 20 parts of hydroxybutyl methacrylate; 20 parts of tricyclodecane dimethanol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2.5 portions of the mixture is added into a stirring kettle and stirred. During the stirring process, the temperature was raised to 60 ℃. After the temperature reaches 60 ℃, vacuumizing and stirring are carried out, the vacuum degree reaches-0.095 MPa for 30 seconds, and then stirring is continuously carried out for 2 hours. And finally, cooling the reaction kettle to room temperature by using cooling water to prepare the adhesive.
In the embodiment, the surface of the polyether urethane acrylate is not easy to dry, the toxicity is high, the peptization rate is high, and the absorbance is high; morpholine acrylate has strong water solubility, quick surface drying and poor water resistance; the water resistance of the hydroxybutyl methacrylate is good, and the water resistance can be balanced and the product performance can be improved by matching the morpholine acrylate and the hydroxybutyl methacrylate.
Example six:
the components and parts by weight selected in the sixth embodiment are as follows: 50 parts of polybutadiene dimethacrylate; 20 parts of hydroxybutyl methacrylate; 20 parts of neopentyl glycol diacrylate acrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2.5 parts.
The preparation method comprises the following steps: according to the formula, 50 parts of polybutadiene dimethacrylate; 20 parts of hydroxy butyl methacrylate; 20 parts of neopentyl glycol diacrylate acrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2.5 portions of the mixture is added into a stirring kettle and stirred. During the stirring process, the temperature was raised to 60 ℃. After the temperature reaches 60 ℃, vacuumizing and stirring are carried out, the vacuum degree reaches-0.095 MPa for 30 seconds, and then stirring is continuously carried out for 2 hours. And finally, cooling the reaction kettle to room temperature by using cooling water to prepare the adhesive.
In the embodiment, the tripropylene glycol diacrylate has the advantages of low odor and low irritation, so that the prepared adhesive has low odor and low irritation.
Example seven:
the seventh embodiment comprises the following components in parts by weight: 45 parts of polyester type polyurethane acrylate; 20 parts of tetrahydrofuran acrylate; 20 parts of tricyclodecane dimethanol diacrylate; 9 parts of acrylic morpholine; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 parts of (1); and (5) 0.5 parts of one.
The preparation method comprises the following steps: according to the formula, 45 parts of polyester urethane acrylate; 20 parts of tetrahydrofuran acrylate; 20 parts of tricyclodecane dimethanol diacrylate; 9 parts of acrylic morpholine; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 parts of (1); one0.5 part is added into a stirring kettle and stirred. During the stirring process, the temperature was raised to 60 ℃. After the temperature reaches 60 ℃, vacuumizing and stirring are carried out, the vacuum degree reaches-0.095 MPa for 30 seconds, and then stirring is continuously carried out for 2 hours. And finally, cooling the reaction kettle to room temperature by using cooling water to prepare the adhesive.
In the embodiment, the tetrahydrofuran acrylate can be well used for plastic bonding, the bonding property is very good, but the anaphylaxis is strong, and the toxicity is high; by matching the tetrahydrofuran acrylate with the tricyclodecane dimethanol diacrylate, the adhesive property is ensured, the toxicity of the product can be reduced, and the product still has higher toxicity, so that the product in the embodiment can be well used for bonding medical equipment which is not in contact with a human body.
In the present application, a resin urethane acrylate having a small water resistance and a small curing oxygen inhibition effect is mainly used, and particularly, a polycarbonate resin, a polybutadiene dimethacrylate, and a polytetrahydrofuran ether resin are preferably used as a resin of a main body to improve the water elution resistance of the main body. This is mainly due to two aspects: (1) the main body resins have excellent water resistance and are not easy to hydrolyze; (2) the material has small anti-oxygen polymerization inhibition effect, and can well solve the problem of quenching and inactivation of free radicals and oxygen in the curing process, thereby solving the problem that the micromolecules at the position of the colloid after being exposed in the air are not cured and dry, because the probability of precipitation of the uncured micromolecules in the water environment is increased, and the toxicity is higher.
In addition, in the present application, a diluent monomer having excellent water resistance, such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc., is selected and used, wherein hydroxyethyl methacrylate is the most preferable diluent monomer, but its oxygen inhibition is relatively significant and reaction speed is slow, so that a monofunctional isobornyl acrylate which is rapidly cured and a polyfunctional monomer are required to increase the reaction degree and reduce the oxygen inhibition effect, thereby improving water resistance and dissolution resistance. Among them, polyfunctional tricyclodecane dimethanol diacrylate (low toxicity) and tripropylene glycol diacrylate are preferable. Because the monofunctional monomer has low reaction activity, mild reaction, small cage wall effect of active free radicals, high reaction conversion rate, less dissolution and strong bonding; the multifunctional monomer has high mechanical strength, small smell, fast reaction, full crosslinking, great shrinkage, poor adhesion and low reaction conversion rate, and has partial molecule incapable of reacting owing to cage wall effect, so that two or several kinds of different functional monomers are combined and balanced.
Furthermore, the organic amine accelerator is selected to improve the overall reaction speed of the product, improve the crosslinking density and reduce the dissolution rate, and meanwhile, the organic amine selects a molecular structure with high molecular weight and reaction activity to reduce the inherent toxicity of the amine and improve the biocompatibility, so that the low-migration toxicity product is finally obtained. And moreover, the use of the coupling agent can further improve the hydrolytic stability, and the coupling agent is mostly a silane coupling agent and improves the water resistance through hydrolysis reaction with water.
In addition, the photoinitiator which is low in residual fragments and precipitation and is applied to the UV printing ink in the fields of food, cigarette packets and the like is selected, and the traditional cracking photoinitiator is replaced by the hydrogen-extracting initiator and the macromolecular initiator, so that the use of the amount of the initiator, the precipitation of cracking fragments and the migration toxicity are reduced.
In the above embodiments, the collocation and use of the resin and the acrylate reactive diluent are preferred, and particularly, the acrylate reactive diluent preferably adopts more than three different collocations. The hydroxyethyl methacrylate has excellent water resistance, but the oxygen inhibition is obvious and the reaction speed is slow, so that the reactivity is improved and the oxygen inhibition effect is reduced by matching monofunctional isobornyl acrylate capable of being quickly cured and polyfunctional monomers (such as tripropylene glycol diacrylate and tricyclodecane dimethanol diacrylate) to balance.
In the above examples, the following components may be used instead of hydroxyethyl methacrylate: hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate. Isobornyl acrylate may also be replaced by the following components: isobornyl methacrylate. The tricyclodecane dimethanol diacrylate can also be replaced by the following components: trimethylolpropane triacrylate, neopentyl glycol diacrylate, dipentaerythritol tetraacrylate.
In the above embodiments, the coupling agent mainly improves the water resistance of the adhesive. Besides KH-560, KH-570, the following grades of photoinitiators can be selected as coupling agents: KH-550, Z-6032, Z-6300 and Z-6076. Besides one and BP, the photoinitiator can also be selected from the following grades of coupling agents: 184. 1108, 819, 1173, BP, 379, 369, 907, ITX, 651.
The above examples were tested for their relevant performance, with reference to GB8368-2018 "Disposable infusion set for gravity transfusion", GB8369 "Disposable blood transfusion set", and GB/T14233.1-2008 "test methods for medical transfusion, blood transfusion, and injection set", part 1: chemical analysis method, GB15810-2019 sterile syringe for one-time use, GB15811-2016 sterile injection for one-time use, and the like.
The following are the results of testing the adhesives of examples 1-7. The test method comprises the following steps:
(1) bonding and drawing force:
the test mode is as follows: the number 7 needle is over 60N, and the needle is kept for 5min without needle drop.
The test mode is as follows: no. 7 needle is 60N or more, and 100pcs of needle is not dropped, and the needle is not dropped by 100%.
And (3) testing results: the adhesives of examples 1-6 can achieve adhesion of PVC conduit more than 50N.
(2) And (3) toxicity testing: grade of cytotoxic, slightly toxic (reference FDA10993-5)
The following are the cytotoxicity tests of the products in the examples.
The test was performed according to ISO 10993-5:2009 part 5 of the biological evaluation of medical devices: the requirement of in vitro cytotoxicity test is that the medical material leaching liquor is contacted with cultured cells, and the toxic effect of the test sample on in vitro cells is evaluated.
Cell lines: NIH 3T3 fibroblasts.
A sample to be tested: sample preparation: UV light curable film (<0.5 mm); specification and model number: 1,2,3,4,5,6 and 7 are UV adhesive films; positive control: powder-free latex gloves; storage conditions were as follows: and (4) room temperature.
The test method comprises the following steps:
1. the sterilization method comprises the following steps: ultraviolet irradiation, respectively irradiating the upper and lower surfaces of the sample for 6h,
2. leaching solvent: L-DMEM containing 10% FBS, 1% streptomycin (100unit/mL penicillin, 100. mu.g/mLstreptomycin)
Leaching proportion: (1-5,7 samples cut into 1X 1cm, No. 6 samples cut into small pieces)
| Sample (I) | Proportion of leaching | Amount of sample | Volume of leach liquor | Extraction conditions |
| Sample to be tested 1-7 | 6cm2/mL | 6cm2 | 1mL | 37℃，24h |
| Blank control | — | — | 1mL | 37℃，24h |
| Positive control | 6cm2/mL | 6cm2 | 1mL | 37℃，24h |
3. And (3) testing:
(1) sample leaching (three replicates);
(2)3T3 cells were cultured in 96-well plates for 24h at 1X 104 cell/well;
(3) absorbing supernatant in the holes, adding 200 mu L of sample leaching liquor into each hole, and culturing for 24h and 48h respectively;
(4) culturing to a set time point, adding 20 mu L of MTT solution (5mg/mL) into each hole, and continuing culturing for 4 h;
(5) the culture solution is aspirated, 200 mu L DMSO is added, and the crystals are completely dissolved by shaking at 200rpm for 10 min;
(6) the relative cell proliferation Rate (RGD) was calculated using 490nm as the detection wavelength and the absorbance of the blank control as 100%.
Fifth, test results (examples 1 to 7)
24h:
| Sample (I) | Blank space | Positive for | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| RGD(％) | 100 | 14.8 | 88.5 | 102.2 | 106.7 | 25 | 43.5 | 128.7 | 39.8 |
48h:
| Sample (I) | Blank space | Positive for | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| RGD(％) | 100 | 8.0 | 97.7 | 86.5 | 80.0 | 8.94 | 10.2 | 89.9 | 9.6 |
In the present application, the use and combination of monomers is subject to constant research and development and, in particular, each monomer has its advantages and limitations: the hydroxyethyl methacrylate alone has high curing hardness, poor surface dryness, slow reaction speed and good water resistance; the tricyclodecane dimethanol diacrylate ester is independently used for curing, so that the cured product is hard and crisp, has good surface dryness, fast reaction and low toxicity; the single use of isobornyl acrylate has high curing hardness, poor surface dryness, high reaction speed and high strength; the single use of the hydroxy butyl methacrylate has slow curing, poor surface dryness and larger smell than the hydroxyethyl methacrylate; the single use of the tetrahydrofuran acrylate has the advantages of fast curing, good surface drying, soft curing, excellent plastic adhesive force, large smell, obvious allergy and large toxicity; the single use of the dimethylacrylamide has the advantages of fast curing, poor surface dryness, high strength, obvious allergy and high toxicity; the single use of the tripropylene glycol diacrylate has the advantages of quick curing, general surface drying, brittle curing, low odor and low irritation. Therefore, adopt multiple different monomer to use in this application mixedly, get the strong point and offset the weak point, make the performance of product more balanced, optimize the product.
As mentioned above, the invention provides an environment-friendly ultraviolet curing adhesive product and a preparation method thereof, which are used for assembling and bonding medical consumables and have the advantages of low biotoxicity, low dissolution, low migration toxicity and low irritation.
The scope of the present invention includes, but is not limited to, the above embodiments, and the present invention is defined by the appended claims, and any alterations, modifications, and improvements that may occur to those skilled in the art are all within the scope of the present invention.
Claims (8)
1. The high-performance low-toxicity medical UV adhesive is characterized by comprising the following components in parts by weight: 40-50 parts of polyurethane acrylate resin; 40-55 parts of low-molecular acrylate reactive diluent; 1-3 parts of an initiation accelerator; 1-10 parts of a coupling agent; 0.1-5 parts of a photoinitiator;
wherein:
the polyurethane acrylate is one or more of polyester polyurethane acrylate, polyether polyurethane acrylate, polybutadiene dimethacrylate and polycarbonate polyurethane acrylate resin;
the low molecular acrylate reactive diluent is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl methacrylate, phenoxyethyl methacrylate, dicyclopentanyl methacrylate, 1, 6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, propoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, dipentaerythritol tetraacrylate, acrylic morpholine and dimethylacrylamide;
the initiation accelerator is an organic amine accelerator.
2. The high-performance low-toxicity medical UV adhesive according to claim 1, wherein the photoinitiator is at least one of 184, 1108, 819, 1173, 379, 369, 907, ITX, 651, BP and one.
3. The high-performance low-toxicity medical UV adhesive according to claim 1, wherein the coupling agent is at least one of KH-550, KH-560, KH-570, Z-6032, Z-6300 and Z-6076.
4. The high-performance low-toxicity medical UV adhesive is characterized by comprising the following components in parts by weight: 40-50 parts of polycarbonate urethane acrylate resin with the molecular weight of 4000; 18-20 parts of hydroxyethyl methacrylate; 10-15 parts of isobornyl acrylate; 5-10 parts of tripropylene glycol diacrylate; 6-10 parts of tricyclodecane dimethanol diacrylate; 2-3 parts of an organic amine accelerator; 0.5-1.5 parts of silane coupling agent; 1-3 parts of a photoinitiator;
wherein: the photoinitiator is at least one of one, BP and CQ; the silane coupling agent is at least one of KH-550, KH-560 and KH-570.
5. The high-performance low-toxicity medical UV adhesive is characterized by comprising the following components in parts by weight: 50 parts of polyester type polyurethane acrylate; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP 2 parts, and one0.5 part.
6. The high-performance low-toxicity medical UV adhesive is characterized by comprising the following components in parts by weight: 25 parts of polycarbonate urethane acrylate resin; polyester urethane acrylate 25; 20 parts of hydroxyethyl methacrylate; 10 parts of hydroxybutyl methacrylate; 10 parts of tricyclodecane dimethanol diacrylate; 4 parts of tripropylene glycol diacrylate; 2.5 parts of an organic amine promoter; KH 560: 1 part; BP: 2 portions and 0.5 portion of one.
7. The high-performance low-toxicity medical UV adhesive is characterized by comprising the following components in parts by weight: 50 parts of polybutadiene dimethacrylate; 20 parts of hydroxybutyl methacrylate; 20 parts of neopentyl glycol diacrylate acrylate; 4 parts of tripropylene glycol diacrylate, 2.5 parts of an organic amine accelerator; KH 560: 1 part; BP: 2.5 parts.
8. The process for preparing a high performance low toxicity medical UV adhesive according to any of claims 1 to 7, characterized in that it comprises the following steps:
s10: sequentially adding the polyurethane acrylate resin, the active acrylate monomer, the coupling agent and the photoinitiator into a stirring kettle according to the mass parts required by the formula, and stirring;
s20: heating to 60 ℃ in the stirring process;
s30: vacuumizing, keeping the vacuum degree to-0.095 MPa for 30 seconds, and continuously stirring for 2 hours;
s40: and cooling to room temperature by using cooling water to prepare the adhesive.
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| CN115044344A (en) * | 2022-07-29 | 2022-09-13 | 浙江国能科技有限公司 | UV hydrolysis adhesive for temporary fixing of microelectronic device and preparation method thereof |
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