CN112280529B - Organosilicon skin adhesive and preparation method thereof - Google Patents
Organosilicon skin adhesive and preparation method thereof Download PDFInfo
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- CN112280529B CN112280529B CN202011026703.3A CN202011026703A CN112280529B CN 112280529 B CN112280529 B CN 112280529B CN 202011026703 A CN202011026703 A CN 202011026703A CN 112280529 B CN112280529 B CN 112280529B
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- silicone oil
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- 239000000853 adhesive Substances 0.000 title claims abstract description 55
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002545 silicone oil Polymers 0.000 claims abstract description 59
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 37
- 229920002050 silicone resin Polymers 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000013037 co-molding Methods 0.000 claims abstract description 3
- 239000003292 glue Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 229920006264 polyurethane film Polymers 0.000 claims description 9
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- -1 polydimethylsiloxane Polymers 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- HMVBQEAJQVQOTI-SOFGYWHQSA-N (e)-3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)\C=C(/C)C#C HMVBQEAJQVQOTI-SOFGYWHQSA-N 0.000 claims description 2
- GRGVQLWQXHFRHO-AATRIKPKSA-N (e)-3-methylpent-3-en-1-yne Chemical compound C\C=C(/C)C#C GRGVQLWQXHFRHO-AATRIKPKSA-N 0.000 claims description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920006267 polyester film Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 15
- 230000035515 penetration Effects 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 231100000344 non-irritating Toxicity 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010059516 Skin toxicity Diseases 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- DDCDEKHXBABHHI-UHFFFAOYSA-N acetylene cyclohexanol Chemical compound C1(CCCCC1)O.C#C DDCDEKHXBABHHI-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- 231100000438 skin toxicity Toxicity 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Abstract
The invention discloses an organosilicon skin gel and a preparation method thereof, wherein the organosilicon skin gel comprises the following raw materials in parts by mass: 100 parts of base adhesive, 0.1 to 5 parts of hydrogen-containing silicone oil, 0.1 to 0.9 part of catalyst, 0.01 to 0.1 part of inhibitor and 0 to 100 parts of environment-friendly solvent; wherein, the base adhesive is obtained by co-molding MQ silicone resin prepolymer solution and vinyl silicone oil. The invention adopts the esterification method and the coforming method to prepare the base adhesive of the organosilicon skin adhesive, which can effectively simplify the process flow, shorten the production period, avoid the use of a large amount of solvents and reduce the cost and the energy consumption. The organosilicon skin adhesive prepared by the base adhesive has the characteristics of good skin affinity, moderate skin viscosity, water resistance, air permeability and repeated tearing and pasting.
Description
Technical Field
The invention relates to the technical field of organic pressure-sensitive adhesives, in particular to an organosilicon skin adhesive and a preparation method thereof.
Background
In the medical field, in order to fix a percutaneous drug delivery system, a detection chip, a wearable device and the like, people often use a pressure-sensitive adhesive tape or an adhesive tape to directly adhere the percutaneous drug delivery system to skin, and the traditional medical pressure-sensitive adhesive mainly uses polyacrylate or polyurethane, and has the defects of low price, wide application, strong skin toxicity, strong irritation, poor air permeability, no sweat resistance and the like, thereby bringing adverse effects to patients.
The organic silicon pressure-sensitive adhesive has more excellent biocompatibility and human body affinity than polyacrylate type and polyurethane type pressure-sensitive adhesives. Silicone pressure-sensitive adhesives on the market can be classified into 2 general categories according to vulcanization system: the peroxide vulcanizing agent is prepared by adding a vulcanizing agent after catalytic polycondensation of hydroxyl silicone oil and MQ silicone resin; the other type is the addition type developed in the 80 th century of the 20 th century, and is obtained by platinum catalytic addition of vinyl silicone oil, hydrogen-containing silicone oil and MQ silicone resin, and in two vulcanization systems, the use of the MQ silicone resin is indispensable, and the MQ silicone resin can play a role in improving the pressure-sensitive adhesive property, providing initial adhesion and holding adhesion and regulating the physical properties of the pressure-sensitive adhesive.
Although the organic silicon pressure-sensitive adhesive has the characteristics of excellent human body affinity, water resistance, air permeability and the like, the organic silicon pressure-sensitive adhesive is easy to cause damage to skin or wounds during tearing due to high bonding strength, and in addition, the organic silicon pressure-sensitive adhesive shows poor flexibility at skin temperature and is easy to cause discomfort of patients. The existing organic silicon skin adhesive is mainly an addition organic silicon pressure-sensitive adhesive, such as a solvent-free organic silicon pressure-sensitive adhesive reported by Chinese patent CN102174309B and a medical addition organic silicon pressure-sensitive adhesive reported by Chinese patent CN107338020, and the organic silicon skin adhesive has better safety and environmental friendliness, but has the defect of causing damage to skin due to higher bonding strength with skin; as reported in international patent WO2008/057155A1 and US patent US0099571A1, the two organosilicon skin adhesives have moderate skin adhesion and skin affinity, but have the defect of poor adhesion with a substrate, so that the currently disclosed patent is not enough to completely meet the requirements of the pharmaceutical industry on the organosilicon skin adhesives.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the organosilicon skin adhesive which is suitable for adhering medical devices to biological substrates (such as skin) and can provide good adhesion with skin and skin-friendly effect, and the preparation method thereof, so as to solve the problems of high skin adhesion strength, poor skin-friendly property, unstable adhesion of the substrates and the like in the prior art.
The invention adopts the following technical scheme:
1. the organic silicon skin glue consists of the following raw materials in parts by mass:
100 parts of base adhesive, 0.1 to 5 parts of hydrogen-containing silicone oil, 0.1 to 0.9 part of catalyst, 0.01 to 0.1 part of inhibitor and 0 to 100 parts of environment-friendly solvent; wherein, the base adhesive is obtained by co-molding MQ silicone resin prepolymer solution and vinyl silicone oil.
The base adhesive formed by the MQ silicone resin prepolymer solution and the vinyl silicone oil is a mixture of the MQ silicone resin polycondensate containing Si-OH groups and the vinyl silicone oil, wherein the MQ silicone resin polycondensate containing Si-OH groups can provide good adhesive force between the organosilicon skin adhesive and the base material.
Further, the preparation method of the MQ silicone resin prepolymer solution comprises the following steps: siO is made of 2 Uniformly mixing 40% of polyethyl silicate, hexamethyldisiloxane, glacial acetic acid and concentrated sulfuric acid, heating to reflux for 4 hours, adding sodium carbonate aqueous solution for neutralization, and layering to obtain an organic phase which is the MQ silicone resin prepolymer solution; wherein, the polysilicate: hexamethyldisiloxane: the molar ratio of glacial acetic acid is 1:0.3 to 0.6:2.0 to 2.4, the dosage of the concentrated sulfuric acid is 0.5 to 3.0 percent of the total mass of the polyethyl silicate and the hexamethyldisiloxane.
Still further, the preparation method of the base adhesive comprises the following steps: the MQ silicone resin prepolymer solution and the vinyl silicone oil are subjected to decompression polycondensation for 2-3 hours at 150-160 ℃ to obtain base gum; wherein, the mass ratio of the MQ silicone resin prepolymer to the vinyl silicone oil in the MQ silicone resin prepolymer solution is 1:0.5 to 20.
Further, the vinyl silicone oil is vinyl-terminated polydimethylsiloxane, and the viscosity is 2000-20000 mPas, preferably 10000-20000 mPas; the vinyl silicone oil contains 0.05 to 0.25 mass percent of vinyl groups, preferably 0.08 to 0.12 mass percent.
Still further, the hydrogen-containing silicone oil has a viscosity of 20 to 50 mPas at 25 ℃ and contains at least 3 Si-H groups in the molecule.
Further, the catalyst is one or more of chloroplatinic acid, chloroplatinic acid/isopropanol complex and silicone oil dilution solution thereof, chloroplatinic acid/olefin siloxane complex and silicone oil dilution solution thereof.
Still further, the inhibitor is one or more of 3-methyl-3-penten-1-yne, 3, 5-dimethyl-3-hexen-1-yne and 3-methyl-1-butyn-1-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol and benzotriazole.
Furthermore, the environment-friendly solvent is ring silicone oil and/or volatile silicone oil. Other non-toxic non-irritating solutions may be substituted in particular applications.
2. The preparation method of the organosilicon skin glue comprises the following steps:
1) Preparing a base adhesive formed by MQ silicone resin prepolymer solution and vinyl silicone oil;
2) Uniformly mixing the base adhesive prepared in the step 1) with an environment-friendly solvent in proportion to obtain a base adhesive solution with certain viscosity;
3) Dividing the base gum solution obtained in the step 2) into two parts, adding a catalyst into one part, and uniformly mixing to obtain a component A; adding hydrogen silicone oil and inhibitor into the other part, and uniformly mixing to obtain a component B, wherein the component A and the component B have equal mass;
specifically, the mass ratio of the base gum to the hydrogen-containing silicone oil to the catalyst to the inhibitor to the environment-friendly solvent is 100:0.1 to 5:0.1 to 0.9:0.01 to 0.1:0 to 100, preferably 100:0.1 to 2:0.1 to 0.4:0.01 to 0.05:20 to 50, more preferably 100:0.1 to 1:0.1 to 0.3:0.01 to 0.03:20 to 25.
4) And uniformly mixing the component A and the component B, coating the mixture on the surface of a substrate through a proper coating process after defoaming, and curing the mixture for 2 to 30 minutes at the temperature of between 120 and 150 ℃ to obtain the organosilicon skin glue with the dry film thickness of between 10 and 300 mu m. The curing time is preferably 3 to 10 minutes. The dry film thickness can be flexibly adjusted according to the actual application requirement, and is preferably 20-50 μm in general.
Specifically, the coating process can be dipping, knife coating, roll coating, spraying, die casting, calendaring, extruding, brushing and the like.
Further, the substrate is one or more of non-woven fabrics, polyolefin films, polyester films, polyurethane films, polyvinyl chloride films, polysiloxane films and polycarbonate.
3. Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the esterification method and the coforming method to prepare the base adhesive of the organosilicon skin adhesive, which can effectively simplify the process flow, shorten the production period, avoid the use of a large amount of solvents and reduce the cost and the energy consumption. More importantly, the polycondensation rate of the MQ silicone resin can be effectively controlled, the generation of indissolvable or insoluble matters is avoided, and the method has obvious effects of improving the yield of the product and improving the compatibility of the MQ silicone resin and vinyl silicone oil; the MQ silicone resin polycondensate containing Si-OH groups in the base adhesive can effectively improve the adhesion performance of the organosilicon skin adhesive and the medical patch base material, thereby solving the problem of poor adhesion between the organosilicon skin adhesive and the base material at present;
(2) The hydrogen-containing silicone oil and the platinum catalyst are added to lead the hydrogen-containing silicone oil and the vinyl silicone oil to generate addition and vulcanization reaction, the vulcanization speed is high, and the curing can be completely performed at 120 ℃ for 3-10 min, thus being very suitable for the rapid production operation of a gluing assembly line. The environment-friendly solvent with little or no dosage can effectively regulate the rheological property of the components, is easy to coat and construct, and simultaneously, the product is safe and environment-friendly, nontoxic and nonirritating.
(3) The organosilicon skin adhesive has the characteristics of good skin affinity, moderate skin viscosity, water resistance, ventilation and repeated tearing and pasting; in addition, moderate cohesive strength may provide good adhesion properties, aiding in the temporary or long-term attachment of test chips, drugs, catheters, and other medical devices to biological substrates (e.g., skin).
Detailed Description
The invention will now be further described with reference to specific embodiments. It should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
Raw materials of organosilicon skin glue
MQ silicone prepolymer solution raw material: polyethylsilicate (according to SiO) 2 The solid content of (1) is calculated to be 40%, the purity is more than or equal to 98%), the purity is more than or equal to 99%, the purity is more than or equal to 98%, the mass fraction is 95-98%, the purity is more than or equal to 96%, and the deionized water.
Vinyl silicone oil a: double-end vinyl silicone oil with the viscosity of 20000 mPas and the vinyl mass fraction of 0.109%;
vinyl silicone oil B: double-end vinyl silicone oil with viscosity of 10000 mPa.s and vinyl mass fraction of 0.132%;
vinyl silicone oil C: double-end vinyl silicone oil with the viscosity of 5000 mPas and the vinyl mass fraction of 0.170%;
vinyl silicone oil D: double-end vinyl silicone oil with the viscosity of 2000 mPas and the vinyl mass fraction of 0.1240%;
hydrogen-containing silicone oil a: side hydrogen-containing silicone oil with viscosity of 40 mPas and mass fraction of hydrogen atoms in Si-H groups of 0.187%;
catalyst: a platinum divinyl tetramethyl disiloxane solution having an effective platinum content of 1000ppm;
inhibitors: 5% of a simethicone mixed solution of acetylene cyclohexanol;
solvent a: hexamethyldisiloxane with purity not less than 99%;
solvent B: cyclopentadimethicone having a purity of 98% or more;
solvent C: the purity of the isomerism dodecane is more than or equal to 98 percent.
Sample preparation and testing
(1) Initial tack was tested using a tape initial tack tester model CNS 11888. The sample can be uniformly mixed according to the formula, and is coated on the surface of the polyurethane film in a blade coating mode after defoamation, and then is solidified, and is cut according to the specification of 80mm wide by 250mm long. The sample was tested according to the requirements of GB/T4852-2002 (inclined spin method), wherein the inclined surface angle was 30℃as the standard angle.
(2) The hold-up viscosity was tested using six sets of hold-up viscosity testers, model BLD 1008D. The test sample is uniformly mixed according to the formula, is coated on the surface of the polyurethane film in a blade coating mode after defoamation, is cured, and is cut according to the specification of 25mm wide by 100mm long. The test sample is tested according to the requirements of GB/T4851-1998, wherein the weight is 1000g, the test time is 72h, and the sliding displacement or the falling time of the test sample is recorded after the specified time is reached.
(3) The peel strength was measured using a tape peel strength tester model PT-1166. The test sample is uniformly mixed according to the formula, is coated on the surface of the polyurethane film in a blade coating mode after defoamation, is cured, and is cut according to the specification of 25mm wide by 250mm long. The test specimens were tested according to the requirements of GB/T2792-1998, in which the test machine carried out a continuous 180℃peel of the test specimens in N/25mm at a rate of rise of 300 mm/min.
(4) The skin re-adhesive sample is prepared by uniformly mixing the skin re-adhesive sample according to a formula, coating the skin re-adhesive sample on the surface of a polyurethane film in a blade coating mode after defoaming, and curing the polyurethane film. The test requires that the skin surface be performed on the same area of the same subject and that the skin be wiped clean with alcohol prior to the test. And (3) taking a small organic silicon skin adhesive test piece, repeatedly sticking the test piece on clean skin until the test piece obviously loses the sticking energy, and recording the sticking times.
(5) Wet steam transmittance according to GB/T12704.2-2009 textile, fabric moisture permeability test method, part 2: positive cup method test in evaporation method. Wherein the test temperature is 38+/-2 ℃ and the relative humidity is 50+/-2%. The test results are expressed as the average of three samples.
(6) Penetration was tested using a penetration tester model SYD-2801C. The samples are uniformly mixed according to the formula (without solvent) in a sample dish (diameter 55mm multiplied by depth 35 mm), defoamed and then placed in a baking oven at 120 ℃ for curing for 2 hours to obtain the composite material. The test specimens were subjected to penetration tests according to the national standard GB/T4509-2010, wherein the cone weight was 102.5.+ -. 0.05g, the penetration time was 5s, the penetration was expressed as 1/10mm, and the test results were expressed as an average of the results of three measurements.
Examples 1 to 5
225g of SiO was charged into a 1L four-necked flask equipped with a strong stirring, a thermometer and a reflux tube 2 The preparation method comprises the steps of uniformly stirring 40% of polyethyl silicate, 97.2g of hexamethyldisiloxane and 198g of glacial acetic acid, adding 4.93g of 98% concentrated sulfuric acid, stirring at normal temperature for 60min, heating, reacting for 4h at the reflux temperature of 76-78 ℃, stopping heating, cooling the reaction liquid to room temperature, adding 148g of saturated sodium carbonate aqueous solution for neutralization, standing and layering to obtain an ethyl acetate solution of 436.85gMQ silicone resin prepolymer, wherein the solid content is 44.11%.
192.69g of vinyl silicone oil A is added into the ethyl acetate solution of the MQ silicone resin prepolymer, the mixture is stirred uniformly, the mixture is heated and is heated up, most of ethyl acetate is distilled out, a vacuum pump is started to pull down when the temperature reaches 150 ℃, the decompression polycondensation reaction is carried out for 2 hours at 150-155 ℃, the heating is stopped, and the hot filtration (300-mesh stainless steel filter screen) is carried out to obtain the base adhesive. 200g of the base gum was dissolved in 50g of the solvent A to prepare a base gum solution. Five portions of 25g of base gum solution are taken respectively, and according to different SiH: siVi value (molar ratio) is added with corresponding amount of hydrogen-containing silicone oil A, then 0.06g of catalyst and 0.02g of inhibitor are added, the mixture is stirred uniformly, defoamed and coated on a polyurethane film, and the polyurethane film is cured for 5min at 120 ℃ to obtain a glue film with the thickness of 20 mu m, and the initial viscosity, the holding viscosity, the peel strength, the skin re-adhesion, the moisture vapor transmission rate and the penetration degree are measured, and the results are shown in Table 1.
Table 1 test results for examples 1-5
Wherein, a of example 1 is adhesive film cohesive failure. And (3) injection: when peel failure occurs in the sealant itself, it is indicated that the adhesive bond strength of the sealant to the adherend is greater than the strength of the sealant itself, referred to as cohesive failure.
From the data in table 1, it was found that: siH: when the SiVi value is low, the cohesive strength is insufficient, and the adhesive is easy to drop; siH: when the SiVi value is high, the peel strength of the skin adhesive is too high, and damage to the skin is easily caused when tearing, and the peel strength is generally less than 2.0N/25 mm. SiH: the SiVi value is in the range of 0.85-1.00, has higher comprehensive performance, and can be suitable for skin glue.
Examples 6 to 9
Ethyl acetate solution of MQ silicone resin prepolymer is prepared according to the method of examples 1-5, four equal parts of vinyl silicone oil A, B, C and D with the same solid content are respectively added, the mixture is stirred uniformly, heated and warmed, most of ethyl acetate is distilled out, a vacuum pump is started to pull down when the temperature reaches 150 ℃, decompression polycondensation reaction is carried out for 1.5 hours at 150-155 ℃, heating is stopped, and the four base adhesives are obtained by filtering while the mixture is hot. 20g of base gum are taken respectively, and the same SiH is added respectively: the SiVi value (equal to 1.00) of hydrogen-containing silicone oil A, 0.06g of catalyst, 0.02g of inhibitor and 5g of solvent A are uniformly stirred, defoamed and coated on a PU film, and cured for 5min at 120 ℃ to obtain a glue film with the dry glue thickness of 20 mu m, and the initial viscosity, the holding viscosity, the peel strength, the skin re-adhesiveness, the moisture vapor transmission rate and the penetration degree are measured, and the results are shown in Table 2.
Table 2 test results for examples 6-9
From the data in table 2, it was found that: at the same SiH: when the SiVi value is reduced, the viscosity is reduced, and when the Vi% is increased, the viscosity and penetration degree of the prepared skin adhesive are reduced, the penetration degree is reduced, the hardness of the adhesive film is increased, and the skin affinity of the skin adhesive is easily reduced.
Examples 10 to 13
A base adhesive was prepared as in example 1, three parts of 20g of the base adhesive were dissolved in 5g of solvents A, B and C, respectively, to prepare three parts of base adhesive solutions, one part of 20g of the adhesive without the solvent was further taken, then 0.25g of hydrogen-containing silicone oil A, 0.06g of catalyst and 0.02g of inhibitor were added, uniformly stirred, defoamed, coated on a PU film, cured at 120℃for 5 minutes, to obtain a film having a dry adhesive thickness of 20. Mu.m, and the initial tackiness, holding tackiness, peel strength, skin re-tackiness, moisture vapor permeability and penetration were measured, and the results are shown in Table 3.
TABLE 3 test results for examples 10-13
From the data in table 3, it was found that: solvents A, B and C can be applied to skin gels under the same formulation conditions, but with increasing boiling point, the cohesive strength of the skin gel decreases slightly, which affects the hold-up to some extent.
Example 14
Taking 17.74g of the base adhesive of the example 1, adding 8.87g of vinyl silicone oil D and 0.16g of catalyst, and uniformly stirring to obtain a skin adhesive component A, wherein the viscosity of the skin adhesive component A is 8300 mPa.s; further, 17.26g of the base gel of example 1 was added with 8.63g of vinyl silicone oil D, 0.83g of hydrogen-containing silicone oil A and 0.05g of an inhibitor, and stirred uniformly to prepare a skin gel component B having a viscosity of 7600 mPas. Taking components A and B with the same mass, uniformly stirring, coating on a PU film after defoaming, and curing for 5min at 120 ℃ to obtain a glue film with the dry glue thickness of 150 mu m, wherein the properties of the obtained skin glue are as follows: initial tack 7#, holding tack 58 seconds, peel strength of 0.935N/25mm, penetration of 174.5, skin re-tack > 50 times.
Comparative example 1
10g of commercially available MQ silicone resin powder was taken, 10g of vinyl silicone oil A, 5g of solvent A, 0.22g of hydrogen-containing silicone oil A0.06g of catalyst and 0.02g of inhibitor were added respectively according to the formulation of example 3, and the mixture was uniformly mixed and defoamed to prepare a sample. The test sample is coated on a PU film, and cured for 5min at 120 ℃ to obtain a glue film with the thickness of 20 mu m, and the properties are determined as follows: initial tack 12#, hold tack 48.65h, peel strength 3.853N/25mm, penetration 68.75, skin re-tack 4 times, and the skin gel sample prepared was translucent in appearance with undissolved particles. It can be seen that the silicone pressure sensitive adhesive prepared by the traditional method has high strength, low penetration and poor skin-friendly property, and is not suitable for skin glue.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (8)
1. The organosilicon skin glue is characterized by comprising the following raw materials in parts by mass:
100 parts of base adhesive, 0.1-5 parts of hydrogen-containing silicone oil, 0.1-0.9 part of catalyst, 0.01-0.1 part of inhibitor and 0-100 parts of environment-friendly solvent; wherein, the base adhesive is obtained by co-molding MQ silicone resin prepolymer solution and vinyl silicone oil; siH: the molar ratio of SiVi is 0.85-1.00; the viscosity of the vinyl silicone oil is 5000-20000 mPas;
specifically, the preparation method of the MQ silicone resin prepolymer solution comprises the following steps: siO is made of 2 Uniformly mixing 40% of polyethyl silicate, hexamethyldisiloxane, glacial acetic acid and concentrated sulfuric acid, heating to reflux for 4 hours, neutralizing, and layering to obtain an organic phase which is the MQ silicone resin prepolymer solution; wherein, the polysilicate: hexamethyldisiloxane: the molar ratio of glacial acetic acid is 1:0.3 to 0.6: 2.0-2.4, wherein the consumption of concentrated sulfuric acid is 0.5-3.0% of the total mass of the polyethyl silicate and the hexamethyldisiloxane; the preparation method of the base adhesive comprises the following steps: the MQ silicone resin prepolymer solution and the vinyl silicone oil are subjected to reduced pressure polycondensation at 150-160 ℃ for 2-3After h, obtaining base adhesive; wherein, the mass ratio of the MQ silicone resin prepolymer to the vinyl silicone oil in the MQ silicone resin prepolymer solution is 1: 0.5-20.
2. The silicone skin gel of claim 1, wherein the vinyl silicone oil is a vinyl-terminated polydimethylsiloxane; the mass percentage of vinyl in the vinyl silicone oil is 0.05-0.25%.
3. The silicone skin gel according to claim 1, wherein the hydrogen-containing silicone oil contains at least 3 Si-H groups in the molecule, and has a viscosity of 20 to 50 mPa-s at 25 ℃.
4. The silicone skin gel of claim 1, wherein the catalyst is one or more of chloroplatinic acid, chloroplatinic acid/isopropanol complex and silicone oil diluted solution thereof, chloroplatinic acid/olefin siloxane complex and silicone oil diluted solution thereof.
5. The silicone skin gel of claim 1, wherein the inhibitor is one or more of 3-methyl-3-penten-1-yne, 3, 5-dimethyl-3-hexen-1-yne, and 3-methyl-1-butyn-1-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, and benzotriazole.
6. The silicone skin gel of claim 1, wherein the environmentally friendly solvent is a cyclic silicone oil and/or a volatile silicone oil.
7. The method for preparing the organic silicon skin glue according to any one of claims 1 to 6, which is characterized by comprising the following steps:
1) Preparing a base adhesive formed by MQ silicone resin prepolymer solution and vinyl silicone oil;
2) Uniformly mixing the base adhesive prepared in the step 1) with an environment-friendly solvent in proportion to obtain a base adhesive solution with certain viscosity;
3) Dividing the base gum solution obtained in the step 2) into two parts, adding a catalyst into one part, and uniformly mixing to obtain a component A; adding hydrogen silicone oil and inhibitor into the other part, and uniformly mixing to obtain a component B, wherein the component A and the component B have equal mass;
4) And uniformly mixing the component A and the component B, coating the mixture on the surface of a substrate through a proper coating process after defoaming, and curing at 120-150 ℃ to obtain the organosilicon skin glue.
8. The method for preparing the silicone skin gel according to claim 7, wherein the substrate is one or more of a nonwoven fabric, a polyolefin film, a polyester film, a polyurethane film, a polyvinyl chloride film, a polysiloxane film, and a polycarbonate.
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| CN111139027A (en) * | 2020-01-10 | 2020-05-12 | 广东标美硅氟新材料有限公司 | Organic silicon pressure-sensitive adhesive-based adhesive and preparation method thereof |
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| CN111139027A (en) * | 2020-01-10 | 2020-05-12 | 广东标美硅氟新材料有限公司 | Organic silicon pressure-sensitive adhesive-based adhesive and preparation method thereof |
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