CN115216259B - Hot-melt pressure-sensitive adhesive for medical application, and preparation method and application thereof - Google Patents
Hot-melt pressure-sensitive adhesive for medical application, and preparation method and application thereof Download PDFInfo
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- CN115216259B CN115216259B CN202210521556.XA CN202210521556A CN115216259B CN 115216259 B CN115216259 B CN 115216259B CN 202210521556 A CN202210521556 A CN 202210521556A CN 115216259 B CN115216259 B CN 115216259B
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 37
- 239000012943 hotmelt Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920006132 styrene block copolymer Polymers 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 19
- 150000003440 styrenes Chemical class 0.000 claims description 18
- 229920002545 silicone oil Polymers 0.000 claims description 15
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 12
- 125000005456 glyceride group Chemical group 0.000 claims description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 12
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- -1 perfluoroalkyl ethyl methacrylate Chemical compound 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 244000064895 Cucumis melo subsp melo Species 0.000 claims 1
- 235000009847 Cucumis melo var cantalupensis Nutrition 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 206010070834 Sensitisation Diseases 0.000 abstract description 2
- 230000008313 sensitization Effects 0.000 abstract description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229940124531 pharmaceutical excipient Drugs 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 102000009123 Fibrin Human genes 0.000 description 1
- 108010073385 Fibrin Proteins 0.000 description 1
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000006550 Liquidambar Nutrition 0.000 description 1
- 241000208682 Liquidambar Species 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229950003499 fibrin Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229940014259 gelatin Drugs 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a hot-melt pressure-sensitive adhesive (IPC (industrial personal computer) classification number: C09/J13308), in particular to a hot-melt pressure-sensitive adhesive for medical application, and a preparation method and application thereof. The raw materials at least comprise the following components in parts by weight: 4-10 parts of SIS, 15-30 parts of modified styrene block copolymer, 1-5 parts of tackifying resin, 5-8 parts of polyisobutylene, 5-15 parts of plasticizer, 6-10 parts of modified hydrogenated ester gum, 3-5 parts of antioxidant and 1-3 parts of zinc oxide. The product prepared by the invention has the advantages of no sensitization, no residue, no holding power and the like, and simultaneously further reduces the low peeling force, does not cause large pulling force to skin during the tearing, and is beneficial to keeping the comfort of use.
Description
Technical Field
The invention relates to a hot-melt pressure-sensitive adhesive (IPC (industrial personal computer) classification number: C09/J13308), in particular to a hot-melt pressure-sensitive adhesive for medical application, and a preparation method and application thereof.
Background
Pressure sensitive adhesives are a type of adhesive that can be firmly adhered to an adherend without the aid of solvents or heat manipulation processes and with only slight pressure applied. The pressure-sensitive adhesive tape has certain initial viscosity and holding viscosity, can be repeatedly used under the condition of no pollution, and has no damage to the surface of an adhered material and no pollution after being peeled.
The patent application CN201810102048.1 prepares a thermal aging resistant hot melt pressure sensitive adhesive and a preparation process, and is prepared by mixing and melting SIS, naphthenic oil, C5 petroleum resin, PIB, coupling, antioxidant and nano inorganic composite ultraviolet absorbent in a certain proportion and in sequence. The prepared hot-melt pressure-sensitive adhesive has longer service life and has the defect of low initial adhesion and low holding adhesion. Patent CN104491922B discloses a hydrophilic polyurethane pressure-sensitive adhesive for skin and a preparation method thereof, wherein the pressure-sensitive adhesive comprises the following components: polyurethane, liquidambar resin, alginate, gelatin, fibrin, plant polysaccharide, methacryloyl ethyl sulfobetaine, triethyl citrate and polyethylene glycol dimethyl ether.
Therefore, the product prepared by the invention has the advantages of no sensitization, no residue, no holding power and the like, and simultaneously further reduces the low T peeling force, does not cause large pulling force on skin during the tearing, and is beneficial to keeping the comfort of use.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a hot-melt pressure-sensitive adhesive for medical application, which comprises the following raw materials in parts by weight: 4-10 parts of SIS, 15-30 parts of modified styrene block copolymer, 1-5 parts of tackifying resin, 5-8 parts of polyisobutylene, 5-15 parts of plasticizer, 6-10 parts of modified hydrogenated ester gum, 3-5 parts of antioxidant and 1-3 parts of zinc oxide.
Preferably, the hot-melt pressure-sensitive adhesive comprises the following raw materials in parts by weight: 5-8 parts of SIS, 20-25 parts of modified styrene block copolymer, 2-3 parts of tackifying resin, 6-7 parts of polyisobutylene, 8-12 parts of plasticizer, 7-9 parts of modified hydrogenated ester gum, 3-5 parts of antioxidant and 1-3 parts of zinc oxide.
Preferably, the SIS is a styrene-isoprene-styrene block copolymer. The SIS has a styrene content of 15% and is commercially available, for example, D-1107C from Korea polymers, inc.
Preferably, the modified styrene block copolymer is prepared by modifying a styrene-butadiene-styrene block copolymer by a silicone oil modifier and perfluoroalkyl ethyl methacrylate; the styrene-butadiene-styrene block copolymer was purchased from D-1155J, manufactured by Koteng polymers Co., U.S.A.; the silicone oil modifier is vinyl silicone oil.
Preferably, the weight ratio of the styrene-butadiene-styrene block copolymer, the silicone oil modifier and the perfluoroalkyl ethyl methacrylate is 1: (0.1-0.2): (0.1-0.15).
Preferably, the preparation steps of the modified styrenic block copolymer comprise the following steps: (1) Uniformly mixing a styrene-butadiene-styrene block copolymer and a silicone oil modifier, and stirring for 3-5 hours at 80-90 ℃ under the protection of nitrogen to obtain a mixture 1; (2) And adding perfluoroalkyl ethyl methacrylate into the mixture 1, and performing ultrasonic emulsification to obtain the modified styrene block copolymer.
The modified styrene block copolymer is added in the invention, so that the peeling strength is greatly reduced, and the ultra-low T-shaped peeling force is obtained. The applicant speculates that: when the silicone oil modifier modifies the styrene-butadiene-styrene block copolymer, the silicon component in the modified styrene block copolymer and the vinyl group of the introduced carbon-carbon double bond repel each other, so that the "T" peeling force is reduced. In addition, the silicon content of the surface of the adhesive layer is greatly increased, and the peel strength of the silicone oil chain segment is greatly reduced due to the characteristic of small polarity, so that the ultra-low T-shaped peel force can be obtained.
Further preferably, the weight ratio of the SIS to the modified styrenic block copolymer is (0.25 to 0.35): 1.
The application improves the holding viscosity of the hot-melt pressure-sensitive adhesive by limiting the weight ratio of SIS to the modified styrene block copolymer. During the experiment the applicant speculates that: when the SIS content is small, the cohesive strength is small, so that the viscosity is correspondingly reduced, cohesive failure forms such as fracture of the hot-melt pressure-sensitive adhesive can occur during peeling, but as the SIS content is increased, the cohesive strength is increased, the viscosity of the hot-melt pressure-sensitive adhesive also tends to be increased, the surface wettability is reduced, the T-shaped peeling force is increased, and large pulling force is caused to the skin during tearing, so that the comfort of use is maintained.
Preferably, the tackifying resin is selected from one or more of DCPD resin, C9 modified DCPD resin, hydrogenated DCPD petroleum resin, and the like.
Further preferably, the tackifying resin is a DCPD resin, and the softening point of the DCPD resin is 90-108 ℃; the specific gravity of the DCPD resin is 1.02-1.09, and the acid value of the DCPD resin is 0.3-0.5, and the DCPD resin is commercially available, such as a thermal polymerization resin sold by Shandong Cheng Ruilin New Material Co., ltd.
Preferably, the polyisobutylene is purchased from pb2400 sold by cantonese chemical technology limited.
Preferably, the plasticizer is one or more of naphthenic oil, white oil, paraffin oil, castor oil and the like.
Further preferably, the plasticizer is a naphthenic oil, commercially available, such as naphthenic oil K30 sold by Hongtai petrochemical Co., ltd.
Preferably, the modified hydrogenated ester gum is a stearic acid modified rosin glyceride. The rosin glyceride was purchased from Shenzhen Lefu Biotechnology Co.
Preferably, the preparation steps of the modified hydrogenated ester gum are as follows: the rosin glyceride powder was mixed with stearic acid and incubated at 240℃for 6h.
The addition of the modified hydrogenated ester adhesive improves the compatibility of the tackifying resin, SIS and the modified styrene block copolymer, and effectively improves the holding viscosity on the basis of ensuring good cohesive strength of the pressure-sensitive adhesive. Applicant speculates that: when the modified rosin glyceride is compatible with SIS and the modified styrene block copolymer, the modified rosin glyceride can be inserted into a network structure in the system, so that the effect of swelling the modified rosin glyceride is achieved, and the modulus of the whole system is reduced. The pressure-sensitive adhesive can be rapidly spread on an adherend under a small pressure, and meanwhile, when the pressure-sensitive adhesive is spread and wetted on the surface of the adherend, the polar groups of the modified hydrogenated ester adhesive enable the adsorption of the pressure-sensitive adhesive and the adherend to be easier, the molecular acting force to be larger, the holding viscosity to be more obvious and the holding viscosity to be larger.
Further preferably, the weight ratio of the stearic acid to the rosin glyceride powder is (0.15-0.2): 1.
preferably, the weight ratio of the tackifying resin to the modified hydrogenated ester gum is 1: (3.5-4.5).
The invention effectively improves the holding viscosity of the pressure-sensitive adhesive by limiting the weight ratio of the tackifying resin and the modified hydrogenated ester adhesive on the basis of ensuring the good cohesive strength of the pressure-sensitive adhesive. The applicant guesses that adding tackifying resin and modified hydrogenated ester gum into the system can not only improve the viscosity and wettability of the hot melt adhesive, but also improve the surface contact effect and the characteristic adhesive property, and obtain ideal balance among viscosity, cohesive strength and interfacial strength.
Preferably, the antioxidant is one or more of phenolic antioxidants, phosphorus antioxidants and the like.
Further preferably, the antioxidant is a mixture of antioxidants 1010, 168, all purchased from basf, germany.
Further preferably, the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:1.
Preferably, the zinc oxide is purchased from Shanxi brocade pharmaceutical excipients Co.
The second aspect of the invention provides a hot-melt pressure-sensitive adhesive for medical application and a preparation method thereof:
(1) Adding 50wt% of tackifying resin, polyisobutylene, plasticizer, modified hydrogenated ester gum, antioxidant and zinc oxide into a kneader according to SIS;
(2) Heating the kneader to 150-180 ℃, preserving heat for 20-40 minutes, adding the rest tackifying resin and the modified styrene block copolymer into the kneader, kneading for 30-60 minutes at 150-180 ℃, melting and mixing uniformly, and cooling to room temperature.
The beneficial effects are that:
1. the modified styrene block copolymer is added in the invention, so that the peeling strength is greatly reduced, and the ultra-low T-shaped peeling force is obtained.
2. The application improves the holding viscosity of the hot-melt pressure-sensitive adhesive by limiting the weight ratio of SIS to the modified styrene block copolymer.
3. The addition of the modified hydrogenated ester adhesive improves the compatibility of the tackifying resin, SIS and the modified styrene block copolymer, and effectively improves the holding viscosity on the basis of ensuring good cohesive strength of the pressure-sensitive adhesive.
4. The invention effectively improves the holding viscosity of the pressure-sensitive adhesive by limiting the weight ratio of the DCPD resin and the modified hydrogenated ester adhesive on the basis of ensuring the good cohesive strength of the pressure-sensitive adhesive.
5. The addition of the silver ion-loaded zinc oxide effectively ensures the antibacterial property of the pressure-sensitive hot melt adhesive, improves the primary bonding effect and increases the sealing property and the seepage resistance of the product.
Detailed Description
Examples
Example 1
The embodiment 1 of the invention provides a hot-melt pressure-sensitive adhesive for medical application, which comprises the following raw materials in parts by weight: 6 parts of SIS, 22 parts of modified styrene block copolymer, 2 parts of tackifying resin, 6 parts of polyisobutene, 10 parts of plasticizer, 8 parts of modified hydrogenated ester gum, 4 parts of antioxidant and 2 parts of zinc oxide.
The styrene content of SIS in this example was 15% and was purchased from D-1107C, a Keteng Polymer company, USA.
The tackifying resin in this implementation is a DCPD resin, a heat-curable resin purchased from shandong Cheng Ruilin new materials limited.
The polyisobutylene in this implementation was purchased from pb2400 of cantonese chemical technology limited.
The plasticizer in this embodiment is naphthenic oil, which is commercially available as naphthenic oil K30 from Hongtai petrochemical Co., ltd.
The antioxidants in this embodiment are antioxidant 1010, a mixture of antioxidants 168, all purchased from basf, germany.
In this embodiment, the weight ratio of antioxidant 1010 to antioxidant 168 is 1:1.
Preferably, the zinc oxide is purchased from Shanxi brocade pharmaceutical excipients Co.
The preparation of the modified styrenic block copolymer in this example comprises the following steps: (1) Uniformly mixing a styrene-butadiene-styrene block copolymer and a silicone oil modifier, and stirring at 85 ℃ for 4 hours under the protection of nitrogen to obtain a mixture 1; (2) And adding perfluoroalkyl ethyl methacrylate into the mixture 1, and performing ultrasonic emulsification to obtain the modified styrene block copolymer.
The styrene-butadiene-styrene block copolymer of this example was purchased from D-1155J, manufactured by Kort Polymer Co., U.S.A.; the silicone oil modifier is vinyl silicone oil.
The weight ratio of the styrene-butadiene-styrene block copolymer, vinyl silicone oil and perfluoroalkyl ethyl methacrylate in this example was 1:0.15:0.1.
the modified hydrogenated ester gum in this embodiment is a stearic acid modified rosin glyceride. The rosin glyceride was purchased from Shenzhen Lefu Biotechnology Co.
The preparation steps of the modified hydrogenated ester gum in the embodiment are as follows: the rosin glyceride powder was mixed with stearic acid and incubated at 240℃for 6h.
The method for preparing the pulp molded product in the embodiment comprises the following steps:
(1) Leading the plant paper pulp and water into a pulper barrel for pulping for 30min for standby;
(2) Mixing pulped paper pulp and filler, introducing the mixture into a stirrer, stirring the mixture for 30min at a rotating speed of 900r/min, adding alkyl ketene dimer, heating to 53 ℃, stirring and heating, and preserving heat to obtain a mixture I;
(3) Mixing polyvinyl alcohol, a reinforcing agent and water, introducing into a mixing mill, heating to 90 ℃, and cooling to normal temperature to obtain a mixture II;
(4) Introducing the mixture I and the mixture II into a mixer, heating and stirring until the mixture is sticky, stopping heating, introducing a waterproof agent, and stirring and mixing uniformly to obtain a mixture III;
(5) And (3) introducing the mixture III into a die, drying and dehydrating at high temperature, and performing compression molding and cutting to obtain a finished product.
A second aspect of the present embodiment provides a hot-melt pressure-sensitive adhesive for medical application and a method for preparing the same:
(1) Adding 50wt% of tackifying resin, polyisobutylene, plasticizer, modified hydrogenated ester gum, antioxidant and zinc oxide into a kneader according to SIS;
(2) The kneader is heated to 170 ℃, kept at the temperature for 30 minutes, and then added into the kneader together with the modified styrenic block copolymer by the rest 50wt% of tackifying resin, and kneaded for 50 minutes at 170 ℃, and then the mixture is melted and mixed uniformly, and cooled to room temperature.
Example 2
The embodiment of example 2 is the same as that of example 1 except that zinc oxide is added in an amount of 3 parts in example 2.
Example 3
Embodiment 3 is the same as embodiment 1; except that the antioxidant in example 3 was added in an amount of 5 parts.
Comparative example 1
The embodiment of comparative example 1 is the same as example 1; in contrast, the addition amount of the tackifying resin in comparative example 1 was 7 parts.
Comparative example 2
The embodiment of comparative example 2 is the same as example 1; except that the amount of SIS added in comparative example 2 was 2 parts.
Comparative example 3
The embodiment of comparative example 3 is the same as example 1; in contrast, an unmodified styrenic block copolymer was used in comparative example 3.
Performance test data
(1) Kinematic viscosity: viscosity was determined in a conventional manner using an SNB-2-J rotational viscometer.
(2) Softening point: the softening point is determined in a conventional manner according to ASTM E28-2014. The equipment model is SD-0606T.
(3) Holding viscosity: according to GB/T4851-1998 standard, the pressure-sensitive adhesive tape is cut into strips for later use, the cut strips are stuck on a clean stainless steel plate, and the strips are tightly stuck by a pressing roller. And placing the prepared stainless steel plate at the temperature of 23 ℃ for 20min, then hanging the stainless steel plate on an experiment frame of a viscosity-maintaining instrument, hanging a weight below the stainless steel plate until the pressure sensitive adhesive slides up and down to completely fall off under the driving of the weight, and keeping the direction of the stainless steel plate and the direction of the acting force of the weight in the same direction all the time in the whole process. The holding viscosity of the pressure sensitive adhesive can be judged according to the time reading on the holding viscosity instrument.
(4) "T" peel force test: the measurement was carried out according to GB/T2791-1995.
Table 1 shows the physical properties of the hot-melt pressure-sensitive adhesive prepared in example 1.
TABLE 1
Table 2 shows the pressure-sensitive adhesive tapes prepared in examples 1 to 3 and comparative examples 1 to 3, which were prepared by melt-coating with white cotton cloth as a base material.
TABLE 2
Claims (1)
1. The hot-melt pressure-sensitive adhesive for medical application is characterized by comprising the following raw materials in parts by weight: 6 parts of SIS, 22 parts of modified styrene block copolymer, 2 parts of tackifying resin, 6 parts of polyisobutene, 10 parts of plasticizer, 8 parts of modified hydrogenated ester gum, 4 parts of antioxidant and 2 parts of zinc oxide;
the SIS has a styrene content of 15% and a model D-1107C, and is purchased from Korea polymers Co., USA;
the tackifying resin is DCPD resin, and is a heat-polymerized resin purchased from Shandong Cheng Ruilin New Material Co., ltd;
polyisobutene model pb2400, purchased from cantaloupe chemical technologies limited;
the plasticizer is naphthenic oil K30, which is purchased from Hongtai petrochemical Co., ltd;
the antioxidant is antioxidant 1010, a mixture of antioxidants 168, and the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:1, and the antioxidants are purchased from Basoff company of Germany;
the zinc oxide is purchased from Shanxi brocade medical auxiliary materials limited company;
the preparation of the modified styrenic block copolymer comprises the following steps: (1) Uniformly mixing a styrene-butadiene-styrene block copolymer and a silicone oil modifier, and stirring at 85 ℃ for 4 hours under the protection of nitrogen to obtain a mixture 1; (2) Adding perfluoroalkyl ethyl methacrylate into the mixture 1, and performing ultrasonic emulsification to obtain a modified styrene block copolymer;
the model of the styrene-butadiene-styrene block copolymer is D-1155J, and the silicone oil modifier is vinyl silicone oil;
the weight ratio of the styrene-butadiene-styrene block copolymer, the vinyl silicone oil and the perfluoroalkyl ethyl methacrylate is 1:0.15:0.1;
the modified hydrogenated ester gum is stearic acid modified rosin glyceride purchased from Shenzhen Lefu biotechnology Co., ltd; the preparation method of the modified hydrogenated ester gum comprises the following steps: mixing rosin glyceride powder with stearic acid, and preserving the temperature at 240 ℃ for 6 hours;
the preparation method of the hot-melt pressure-sensitive adhesive for medical application comprises the following steps:
(1) Adding SIS,50wt% of tackifying resin, polyisobutylene, plasticizer, modified hydrogenated ester gum, antioxidant and zinc oxide into a kneader;
(2) The kneader is heated to 170 ℃, kept at the temperature for 30 minutes, and then 50 percent of tackifying resin and the modified styrene block copolymer are added into the kneader together, and kneaded for 50 minutes at 170 ℃, melted and mixed uniformly and cooled to room temperature.
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| CN102504735A (en) * | 2011-10-13 | 2012-06-20 | 杨志 | Hot melt pressure sensitive adhesive and preparation method thereof |
| CN110437778A (en) * | 2019-09-20 | 2019-11-12 | 淄博鲁华泓锦新材料股份有限公司 | Adhesive tape hot-fusible pressure-sensitive adhesive and preparation method thereof |
| CN111019575A (en) * | 2019-12-19 | 2020-04-17 | 浙江金嘉科技有限公司 | High-temperature-resistant high-peeling-resistance hot-melt pressure-sensitive adhesive and preparation method thereof |
| CN111995973A (en) * | 2020-07-16 | 2020-11-27 | 嘉好(太仓)新材料股份有限公司 | Low-peeling-force hot-melt pressure-sensitive adhesive special for white cotton cloth application and preparation method thereof |
| CN114163954A (en) * | 2021-12-14 | 2022-03-11 | 佛山市南海骏驰新材料有限公司 | Hot-melt pressure-sensitive adhesive for RFID (radio frequency identification) electronic tag and preparation method thereof |
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| CN102504735A (en) * | 2011-10-13 | 2012-06-20 | 杨志 | Hot melt pressure sensitive adhesive and preparation method thereof |
| CN110437778A (en) * | 2019-09-20 | 2019-11-12 | 淄博鲁华泓锦新材料股份有限公司 | Adhesive tape hot-fusible pressure-sensitive adhesive and preparation method thereof |
| CN111019575A (en) * | 2019-12-19 | 2020-04-17 | 浙江金嘉科技有限公司 | High-temperature-resistant high-peeling-resistance hot-melt pressure-sensitive adhesive and preparation method thereof |
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