CN102719205B - Pressure-sensitive adhesive, pressure-sensitive adhesive tape, preparation method of the pressure-sensitive adhesive tape and medical dressing - Google Patents
Pressure-sensitive adhesive, pressure-sensitive adhesive tape, preparation method of the pressure-sensitive adhesive tape and medical dressing Download PDFInfo
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- CN102719205B CN102719205B CN201110388243.3A CN201110388243A CN102719205B CN 102719205 B CN102719205 B CN 102719205B CN 201110388243 A CN201110388243 A CN 201110388243A CN 102719205 B CN102719205 B CN 102719205B
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Hematology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Materials For Medical Uses (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention relates to a pressure-sensitive adhesive, a pressure-sensitive adhesive tape, a preparation method of the pressure-sensitive adhesive tape and a medical dressing. The pressure-sensitive adhesive is an acrylate pressure-sensitive adhesive and comprises polymers obtained by free radical copolymerization of monomers of a) 10 to 30wt% of one or more hydrophilic acrylate monomers with hydroxyl or ethoxyl, b) 50 to 70wt% of one or more short-chain hydrophobic acrylate monomers having a general structural formula of CH2=CHCOOR1, wherein R1 represents C1-5 alkyl, c) 10 to 35wt% of one or more long-chain hydrophobic acrylate monomers having a general structural formula of CH2=CHCOOR2, wherein R2 represents C6-14 alkyl, and d) 0.5 to 5wt% of one or more propylene monomers which have polar groups and can copolymerize with the monomers shown in a), b) and c).
Description
Technical field
The present invention relates to pressure sensitive adhesive and application thereof, more specifically, relate to pressure-sensitive acrylate and the application as Pressuresensitive Tape and medical dressing thereof.
Background technology
Pressure-sensitive acrylate is widely used in various Pressuresensitive Tape and medical dressing, such as wound dressings.Wound dressings is the articles for use of binding up a wound, in order to cover sore, wound or other materials damaged.The structure of a typical wound dressings comprises one deck and coats pressure sensitive adhesive on backing, and one deck is attached to the release film (see Fig. 1) on glue face.Some wound dressingss are water-fast, but steam-proof, the wound dressings also had is water-fast also saturating vapour both.In recent years, along with the raising of scientific progress and living standards of the people, rear a kind of both water-fast also thoroughly the wound dressings of vapour more and more obtain the attention of people.
WO 84/03837 discloses a kind of solvent-type acrylic ester class pressure sensitive adhesive dry wet both sexes skin all to good bonding effect.There is a large amount of hydrophilic monomers in this pressure sensitive adhesive composition, therefore there is bonding force good under high humidity environment.But this patent document does not relate to the vapour permeability of pressure-sensitive acrylate.
US6,680,113 disclose a kind of dressing pressure sensitive adhesive with higher water vapor transmittance and better viscosity.It is a kind of multilayered structure, includes the film of one or more layers high vapour permeability, and the pressure sensitive adhesive of one deck high viscosity.Its overall water vapor transmittance is 1200g/m
2/ 24hrs/37 DEG C, viscosity is 15g/inch.The high vapour permeability of this dressing pressure sensitive adhesive realizes mainly through one or more layers high vapour permeability film, and the impact of used pressure sensitive adhesive on vapour permeability is not discussed.
At present, also there is no a kind of pressure-sensitive acrylate, both there is high vapour permeability, also there is good viscosity simultaneously, especially when for wound dressings, all have good viscosity to dry, moist skin.
Summary of the invention
The present invention is intended to solve the problems of the technologies described above, and provides one to have high vapour permeability, high-hydrophilic, and has the pressure-sensitive acrylate of excellent adhering.
Particularly, the present invention relates to a kind of pressure-sensitive acrylate, described pressure sensitive adhesive to comprise by following monomer by the free-radical polymerized polymkeric substance formed:
A) hydrophilic acrylate monomer of the hydroxyl or oxyethyl group of .10%-30%, in the gross weight of all monomers by 100%;
B) hydrophobic acrylic acid's esters monomer of the short chain of .50%-70%, in the gross weight of all monomers by 100%; The structural formula of hydrophobic acrylic acid's esters monomer of described short chain is CH
2=CHCOOR
1, R
1it is the alkyl containing 1-5 carbon atom;
C) hydrophobic acrylic acid's esters monomer of the long-chain of .10%-35%, in the gross weight of all monomers by 100%; The structural formula of hydrophobic acrylic acid's esters monomer of described long-chain is CH
2=CHCOOR
2, R
2it is the alkyl containing 6-14 carbon atom;
D) .0.5%-5% can with third vinyl monomer with polar group of above-mentioned monomer a-c copolymerization, in the gross weight of all monomers by 100%.
The present invention respectively selects one or more monomer to be combined by each class from above four class monomers, pressure-sensitive acrylate is formed in the mode of free radicals copolymerization reaction, not only can have good water vapor transmittance, also can to no matter being that dryness or moist skin have good viscosity, simultaneously also can be irritant little, without characteristics such as culls.
The invention still further relates to a kind of Pressuresensitive Tape of high vapour permeability, it comprises the one deck be coated on backing pressure-sensitive acrylate provided by the invention, and described Pressuresensitive Tape is in positive agar diffusion method test, and its water vapor transmittance can reach 1900g/m
2/ 24hrs/37 DEG C (the dry glue being coated with one deck 25 microns on 25 microns of polyurethane films records).
The invention still further relates to a kind of method preparing Pressuresensitive Tape, described method is included on backing and is coated with one deck pressure-sensitive acrylate provided by the invention, and solidifies by making pressure-sensitive acrylate crosslinked.
The present invention also relates to a kind of medical dressing in addition, and it comprises above-mentioned Pressuresensitive Tape, and encloses one deck release film on the glue face of described Pressuresensitive Tape.The initial viscosity of this medical dressing in dry skin is ~ 100g/inch, on moist skin, initial viscosity has ~ 45g/inch, viscosity in dryness or moist skin after 72 hours is ~ 170g/inch, and the viscosity in dryness or moist skin after 168 hours is ~ 110g/inch.(" ~ " used herein represents mean value, because the skin difference of different people is very large, so represent in the mode of averaging the viscosity of skin.)
According to pressure-sensitive acrylate of the present invention (band) and medical dressing, there is high vapour permeability, good viscosity and good wetting ability, and with low cost.Simultaneously it also to have viscosity high, cull is few, to advantages such as skin irritation are low.Even still very high bonding force can be kept under the environment of high humidity.
Accompanying drawing explanation
Fig. 1 is the structure sectional elevation of the present invention's exemplary wound dressing.
Fig. 2 shows the relation of vinylformic acid 2-(2-ethoxyethoxy) ethyl ester (EEEA) monomer ratio and intrinsic viscosity I.V. and water vapor transmittance MVTR.
Fig. 3 shows the inside clinical test results of the viscosity of pressure sensitive adhesive of the present invention.
Fig. 4 is the schematic diagram of water vapor transmittance (MVTR) testing method.
Embodiment
Pressure-sensitive acrylate of the present invention comprises the polymkeric substance formed by following four kinds of monomer copolymerizations:
A). the hydrophilic acrylate monomer of hydroxyl or oxyethyl group;
B). hydrophobic acrylic acid's esters monomer of short chain, its structural formula is CH
2=CHCOOR
1, R
1it is the alkyl containing 1-5 carbon atom;
C). hydrophobic acrylic acid's esters monomer of long-chain, its structural formula is CH
2=CHCOOR
2, R
2it is the alkyl containing 6-14 carbon atom;
D). can with third vinyl monomer with polar group of above-mentioned monomer a-c copolymerization.
Copolymerization process can be conventional free radical polymerisation process.In a specific embodiment, the actual conditions of polyreaction is as follows:
All monomers and solvent are added successively in 1000 gallons of reactors, as shown in Table 2, stir half hour, the speed of stirrer is 70 rpms for monomer and solvent ratios.Logical nitrogen deoxygenation, the time of deoxygenation is approximately 15-30 minute.Then the temperature of material in reactor (monomer, solvent and initiator) is elevated to 59 degrees Celsius.By initiator (such as AIBN) with 1: 10 ratio be dissolved in ethyl acetate, and add (see table two) in material.After about 10-15 minute, reaction starts, and at this moment temperature of charge obviously can raise 1-2 degree Celsius.Control temperature of charge at 60 degrees Celsius, stir speed (S.S.) is 70 rpms, reacts 24 hours, and transformation efficiency at this moment should more than 99%, and reaction terminates.Finally material is cooled to 43 degrees Celsius of dischargings.The polymkeric substance I.V. finally obtained between 0.9-1.1dl/g, weight-average molecular weight Mw at 500,000-900, between 000.
Wherein the measuring method of transformation efficiency is: get about 3 grams of materials, put into 105 degrees Celsius of baking ovens 2 hours, takes out and is placed in drying basin 15 minutes, then weigh.Its formula is
The chemical related in the present invention all represents with abbreviation, and specific explanations is in table one.
The representational chemical that table one is involved in the present invention to be arrived and supplier
The ratio of table two monomer, solvent and initiator, in table, ratio is weight ratio
* note: EtOAc herein includes the EtOAc. for dissolving AIBN
The various monomers being used for pressure-sensitive acrylate of the present invention will be described in detail below.
A) hydrophilic acrylate monomer
As far back as 1984, if William R.Snyder and colleague thereof just propose in WO 84/03837 a kind of have good hydrophilic monomer and other monomer even hydrophobic monomer be polymerized, the polymer generated also with good wetting ability, therefore can improve the viscosity on moist skin greatly.They advise that the weight percent that this monomer accounts for total polymer monomer is 5%-30%.We study and find in the hydrophilic monomer of this class, and hydrophilic acrylate monomer that is hydroxyl or oxyethyl group not only effectively can strengthen the wetting ability of polymkeric substance, can also strengthen its vapour permeability.
Hydrophilic acrylate monomer that is hydroxyl or oxyethyl group of the present invention includes but not limited to: trimethylolpropane diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate, vinylformic acid 2-hydroxy methacrylate (2-HEA), vinylformic acid 4-hydroxyl benzyl ester (4-HBA), vinylformic acid 2-(2-ethoxyethoxy) ethyl ester (EEEA).Most preferably EEEA, 2-HEA and 4-HBA.
In addition, the impact of different types of hydrophilic monomer on vapour permeability is different.As shown in Table 3, when the weight percent of monomer is identical, containing oxyethyl group EEEA than hydroxyl 2-HEA and 4-HBA to the raising better effects if of MVTR a bit.Such as, but consider the impact on other performance of tackiness agent, second-order transition temperature rises and causes holding viscosity decline, and the amount of such hydrophilic monomer should not be too high.As can be seen from figure bis-, for EEEA, when EEEA brings up to 10% from account for total amount of monomer 5%, its MVTR improves 56g/m
2/ 24hrs. but bring up to 22% from 15% as EEEA, its MVTR improve only 5g/m
2/ 24hrs.On the other hand, after EEEA concentration improves, its intrinsic viscosity I.V. also has and significantly rises, and too high I.V. is found to reduce the viscosity to skin surface, comprises tack and holds viscosity.
Consider the balance between high water-permeability and other performances, the ratio of the hydrophilic acrylate monomer of hydroxyl or oxyethyl group preferably accounts for the 10%-30% of the gross weight of all monomers, more preferably 15%-25%.
Table three different hydrophilic monomer is on the impact of water vapor transmittance (MVTR), and in table, ratio is weight ratio
Fig. 4 shows the device of MVTR test and the method for installation testing sample.This MVTR test is according to TMS0759, and carry out temperature 37 DEG C, the PU film of use is the polyurethane film supplied by Bayer.Concrete steps and condition as follows:
1. in vial, load about 50ml water
2. sample is attached on the mucilage glue surface of aluminium foil ring 5, notices that sample should be placed in the center in the oval hole of aluminium foil ring.
3. align with second aluminium foil ring for ensureing, first aluminium foil ring 5 (glue faces up) is put in one plane.Sample 3 is aimed at central authorities, is attached on first aluminium foil ring.Then second aluminium foil ring 2 (glue faces down) is attached on sample 3, the oval hole of two aluminium foil rings is overlapped.With finger by whole for aluminium foil/sample/aluminum foil flattening, note not having fold or space.
4. rubber cradle 4 is placed on (see Fig. 4) on bottleneck, then aluminium foil/sample/aluminium foil assembly is placed on packing ring 4.If sample has gluing, then glue is faced down.(if sample one side is film, and one side is cloth or non-woven fabrics, then faced down by film one).
5. screw on bottle cap 1 lightly, bottle is placed in metal frame, and put it into ageing oven.Ageing oven is by following condition setting, and put 4 hours: 40 DEG C ± 1 DEG C (104 °F ± 1.8 °F), relative humidity is 20% ± 2%.
6. in ageing oven, screw bottle cap 1 (forefinger is placed on above bottle cap and sample, and such sample is meeting and bottle cap level, avoids producing and expands), rubber cradle 4 is placed on definite position.
7. sample is taken out from ageing oven, weighs (initial weight W1) with analytical balance immediately, balance be accurate to 0.01g.
8. bottle is put back to ageing oven, at least place 18 hours.
9. sample is taken out from ageing oven, weighs (final weight W2) with analytical balance immediately, balance be accurate to 0.01g.
10. calculate moisture transmission, unit is g/m
2/ 24hrs
MVTR=(W1-W2)/S/T × 24 hour
W1=initial weight (g)
W2=final weight (g)
Test area (the m of S=sample
2)
T=test period (hour), test period should be greater than 18h.
B) hydrophobic acrylic acid's esters monomer of short chain and hydrophobic acrylic acid's esters monomer of c) long-chain
Except above-mentioned hydrophilic monomer, the present inventor is investigated the vapour permeability of hydrophobic acrylic acid's esters monomer on pressure sensitive adhesive and the impact of viscosity.Find: by hydrophobic acrylic acid's esters monomer two class of the hydrophobic acrylic acid's esters monomer and long-chain that hydrophobic acrylic acid's esters monomer are divided into short chain, and the ratio suitably controlled between the two, can obtain a good balance between MVTR and viscosity.
Hydrophobic acrylic acid's esters monomer of short chain of the present invention refers to that structural formula is CH
2=CHCOOR
1acrylic ester monomer, wherein R
1it is the alkyl containing 1-5 carbon atom.Specific examples includes but not limited to: methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate etc., preferred methyl acrylate, ethyl propenoate, butyl acrylate, most preferably butyl acrylate (BA).
Hydrophobic acrylic acid's esters monomer of long-chain of the present invention refers to that structural formula is CH
2=CHCOOR
2acrylic ester monomer, wherein R
2it is the alkyl containing 6-14 carbon atom.Specific examples includes but not limited to: ethyl acrylate, Isooctyl acrylate monomer, octyl acrylate, decyl acrylate, dodecyl acrylate, tridecyl acrylate etc., preferred ethyl acrylate (2-EHA), Isooctyl acrylate monomer.
Ratio between hydrophobic acrylic acid's esters monomer of hydrophobic acrylic acid's esters monomer of b) short chain of the present invention and c) long-chain has remarkably influenced to the MVTR of pressure sensitive adhesive and viscosity.As shown in Table 4, if keep the content of EEEA constant, improve the ratio of BA and reduce the ratio of 2-EHA, then MVTR will improve a lot.When the weight percent that BA accounts for all monomers brings up to 75 parts from 0, its MVTR is from ~ 1500g/m
2/ 24hrs is elevated to ~ 2200g/m
2/ 24hrs.But its viscosity also has significant decline simultaneously.Therefore, will obtain a good balance between MVTR and viscosity, the ratio of monomer must remain on a suitable scope.The preferred scope of the present invention is: hydrophobic acrylic acid's esters monomer of short chain accounts for the 50%-70% of total monomer weight, most preferably 55%-65%; Hydrophobic acrylic acid's esters monomer of long-chain accounts for the 10%-35% of total monomer weight, most preferably 20%-30%.
Table four BA and 2-EHA is on the impact of MVTR and viscosity
Viscosity testing substrates: stainless steel plate
Viscosity determining procedure: 180 ° of strippings, ASTMD3330
I.V.: intrinsic viscosity, testing method: TM0148
PU film: urethane, Vix Co. Korea S of supplier, 20.3 microns of blank PU films, MVTR3000g/m
2/ 24hrs
MVTR testing method: TMS0759, temperature 37 DEG C
I.V. testing method is specific as follows:
Testing tool: LAUDA Proline PV24
1. the sample that takes a morsel is dissolved in ethyl acetate, is made into and is approximately 0.25g (dry glue)/100 milliliters of (ethyl acetate) solution.
2. the solution of joining in 1 is got the aluminum dish that 25mL puts into a known weight, be placed in 105 DEG C of baking ovens and toast two hours.Taking-up is weighed, and deducts the weight of aluminum dish, obtains the heavy w1 of the dry glue of reality in 25mL solution.
3. getting 9.00 grams of analytically pure ethyl acetate is that standardized liquid flows through instrument kapillary, records the solution of joining in 1 to be got 9.00 grams again by this section of kapillary time used t1. and flow through same section of kapillary, obtains time t2.
4., by actual for solution solid content w1, standardized liquid is by kapillary time t1, and sample inputs corresponding software by kapillary time t2, can obtain the intrinsic viscosity I.V.. of this pressure sensitive adhesive
Viscosity determining procedure: 180 ° of strippings, ASTMD3330, testing tool: IMASS SP-2000
1. prepare the steel plate of a piece 4 inches × 10 inches
2. cut out the sample of 1 inch × 12 inches
3. first use isopropyl alcohol surface of steel plate, to remove dust and dirt.
4. sample is peelled off separate-type paper, glue faces down and is attached to surface of steel plate, uses doctor blade.Because sample is longer than steel plate, so sample one end is exposed at outside steel plate.
5. leave standstill 20 minutes
6. steel plate is horizontally fixed on instrument sample platform, sample is exposed at one end outside steel plate along steel plate direction double flat, and is fixed in instrument clamps.Instrument parameter is set to:
Speed: 12 foot per minute
Test mode: peeling force
Lag time: 2 seconds
Test duration: 5 seconds
7. start test by " start ", automatically stop and record data.
D). can with third vinyl monomer with polar group of above-mentioned monomer a-c copolymerization
Of the present invention can preferably have the third vinyl monomer of high glass-transition temperature with third vinyl monomer with polar group of above-mentioned monomer a-c copolymerization, more preferably there is the third vinyl monomer of carboxyl or amide group, its specific examples includes but not limited to: acrylamide, vinylformic acid, Methacrylamide, methacrylic acid; Preferred acrylamide and vinylformic acid, because their polarity is stronger; Most preferably acrylamide, because its nonirritant.0.5%-5% can be preferably, preferred 1%-3% with the part by weight of the third vinyl monomer in whole monomer with polar group of above-mentioned monomer a-c copolymerization.
Contriver finds, synthesize one and have high water vapor transmittance, high viscosity, the acrylic pressure-sensitive adhesivee of low cull, and monomer whose composition mainly contains four parts.The hydrophilic monomer of the hydroxyl or oxyethyl group of the first, the ratio that they account for whole monomer is 10%-30%.They mainly provide certain vapour permeability, also can improve the cohesive force to moist skin simultaneously; It two is hydrophobic short chain acrylates class monomers, CH
2=CHCOOR
1, R
1be the alkyl containing 1-5 carbon atom, they account for the 50%-70% of the gross weight of all monomers, as methyl acrylate, and ethyl propenoate, butyl acrylate etc.Although this class monomer is considered to hydrophobic usually, compare the acrylate monomer of long-chain, they have better vapour permeability (table four), the balance of adjustable tack and vapour permeability, and provide certain cohesive strength.3rd class is hydrophobic acrylic acid's esters monomer of long-chain, and its structural formula is CH
2=CHCOOR
2, R
2be the alkyl containing 6-14 carbon atom, they account for the 10%-35% of the gross weight of all monomers.The kindliness of these long-chained monomer is good, can strengthen the wetting property of glue, improves initial bonding strength and peeling force, thus improves the viscosity of whole glue.4th class is as acrylamide, vinylformic acid, Methacrylamide, methacrylic acid isopolarity monomer, they with carboxyl or amide group isopolarity group, can bring good cohesive strength to tackiness agent usually, be easy to crosslinked, and energy and bonded base material form firmly hydrogen bond.This class monomer accounts for the gross weight 0.5 ~ 5% of all monomers.
If each class respectively selects one or more monomer to be combined from above four class monomers, with the acrylic acid adhesive that the mode of free radicals copolymerization reaction generates, not only can have good water vapor transmittance, also can to no matter being that dryness or moist skin have good viscosity, simultaneously also can be irritant little, without characteristics such as culls.Formula shown in table five is the preferred several combination of the present invention.
Four kinds of optimization of C/C composites and test result thereof in table five the present invention
* by changing polymeric reaction condition control I.V., I.V. is reduced.
I.V.: intrinsic viscosity, testing method: TM0148
PU film: urethane, Vix Co. Korea S of supplier, 20.3 microns of blank PU films, MVTR3000g/m
2/ 24h
MVTR testing method: TMS0759, temperature 37 DEG C
Tegaderm std, Tegaderm HP and MMD is the product of 3M.
IV-3000 is the product of Smith & Nephew (Xerox's brightness).
As can be seen from Table V, compared with commercially available a few money products, the MVTR-1837g/m of HPA-14/14-L and HPA-12/12-L
2/ 24hrs and 1900g/m
2/ 24hrs will be much higher than the 900g/m of Tegadem std
2the 1100g/m of/24hrs and Tegaderm HP
2/ 24hrs, a little more than the 1700g/m of MMD
2/ 24hrs, lower than the 2700g/m of IV-3000
2/ 24hrs.Major cause lower than IV-3000 is that base material is different with bondline thickness.The bondline thickness of IV-3000 only has 12 microns, is the half of HPA-14/14-L and HPA-12/12-L, and the base material that the ventilation property of base material also provides than supplier Vix Co. is high.MMD have employed the mode of point-like gluing, and dry glue in spot distribution, has very large space can vapour thoroughly on PU film between glue point and glue point.Compared to traditional continuous coating, when using identical pressure sensitive adhesive, the MVTR of adhesive tape greatly can be improved.Even now, and have employed high vapour permeability pressure sensitive adhesive, and uses HPA-14/14-L with HPA-12/12-L of traditional continuous coating to compare, and is still slightly not so good as.And relative to base material, bondline thickness, the Tegaderm std that coating method is all similar, Tegaderm HP, HPA-14/14-L and HPA-12/12-L have obvious advantage on MVTR.
Pressuresensitive Tape and medical dressing:
Acrylic pressure-sensitive adhesivee of the present invention can be widely used in the various adhesive areas needing high water vapor transmittance, comprises industry, medical treatment and family expenses tackiness agent.As the most general a kind of use-pattern, acrylic pressure-sensitive adhesivee of the present invention can be coated on backing to form Pressuresensitive Tape.
Backing can be known conventional backing, such as, and textile fabric, nonwoven fabric, paper or synthetic materials.In order to provide the Pressuresensitive Tape of high water vapor transmittance, backing, except providing a supporting role, also should have high vapour permeability.Such backing can be made up of the material with high vapour permeability, such as polyurethane film.
After acrylic pressure-sensitive adhesivee is coated on backing, need make acrylic pressure-sensitive adhesivee crosslinked and solidify.Described crosslinked, can by realizing with radiation exposure or interpolation linking agent.Described ray, can select gamma rays, also can select electron beam.Described linking agent, can be selected from following one or more: metallic-ion crosslinking agent, aziridine crosslinker, isocyanate crosslinking; The consumption of described linking agent is the 0.01%-5% of the weight accounting for whole monomer.
Acrylic pressure-sensitive adhesivee of the present invention is particularly suitable for medical dressing.When for medical dressing, one deck release film can be enclosed on the glue face of above-mentioned Pressuresensitive Tape, so that extremely light and stable off-type force can be shown for pressure sensitive adhesive.
Release film includes but not limited to: the release film be made up of the cated base material of tool.Described base material includes but not limited to: stationery base material, film class base material, aluminium foil class base material, polyolefin based materials base material.Above-mentioned release film has at least one side to have the coating of a low surface energy, and described coating comprises one or several following compounds: organosilicon, fluorochemical, fluorine-silicon copolymer thing, side chain are the polyolefinic compound of long-chain.Described release film, preferred grammes per square metre 80-120g/m
2between papery release film, there are precious swallow, loparex etc. in supplier.
A typical medical dressing structure is shown in Fig. 1, is followed successively by polyurethane film 1 from top to bottom, pressure sensitive adhesive 2, release film 3.Polyurethane film 1 is supplied by Vix Co. Korea S of supplier, thickness 20.3 microns.Pressure sensitive adhesive 2 is pressure-sensitive acrylate of the present invention, bondline thickness 25 microns, and transfer coating method is coated with.Separate-type paper 3 is 80g one side separate-type paper, and upper Hypon swallow provides.Crosslinking curing and sterilizing gamma ray realize.By Shanghai JPY Ion-Tech Co., Ltd, cobalt source is adopted to carry out cross-linking radiation and sterilizing, dosage range: 25-50kGy.
Inner clinical experiment
In order to better verify the use properties of preferred embodiment in the present invention, carry out inner clinical experiment.Namely in assessment embodiment, sample, in Healthy People service condition with it, observes the MVTR of dressing, viscosity, cull, crimping and skin reaction etc.
With commercial samples Tegaderm std, Tegaderm HP, IV-3000 and MMD does reference, and Sample Preparation Procedure is as follows: select HPA-12, HPA-12L, HPA-14, HPA-14L tetra-formula in the present invention.The coating process adopted is: be first coated in separate-type paper by glue, then coat PU film at Jiao Mianshang.PU thickness is 20.3 μm, and the glue spread of glue is 20g/m
2, thick 25 microns of dry glue.Above-mentioned sample is also crosslinked through conventional gamma sterilization, is then cut into the sample of 2.5 × 8cm, is affixed on volunteer back and carries out clinical experiment.Select 12 volunteers, stochastic distribution is done to pasted sample position.Assessment sample at initial 0h (T0), the viscosity of 72 hours (T72) and 168 hours (T168), cull, crimping and skin reaction.Testing method is as follows:
Step:
1. first clinical study slip-stick artist will clean the skin at experimenter back by the aqueous soup solution of dilution.
2. clinical study slip-stick artist will stick 8 dressing (dryness) (each one of each sample) at experimenter's left dorsal; On the right side of experimenter back, spill a small amount of warm water, then stick other 8 dressing (moist) (each one of each sample), and ASTMD3330 method tests these samples after 5 minutes, is recorded as T0.Sample size is 2.5 × 8cm
2.
3. same dressing is sticked in the position same at experimenter back by clinical study slip-stick artist again.
4. clinical study slip-stick artist will require that experimenter returns IHP testing laboratory after 72 hours, and that assesses all samples floats rate and skin reaction.Half sample can be torn off, assessment viscosity and residual gum content (T72).
5. clinical study slip-stick artist will require that experimenter returned the assessment that sample makees in IHP testing laboratory after 168 hours.Second half sample remaining can be torn off, and rate, viscosity, residual gum content and skin reaction (T168) are floated in assessment.
Fig. 3 shows the result of viscosity clinical trial.Adhesion Test Method is similar to ASTMD3330, only steel plate is changed into human body back, 180 degree of strippings, 12inch/min.In Fig. 3, T0 (Dry) represents the initial viscosity of institute's test sample product in dry skin, T0 (Wet) represents the initial viscosity of institute's test sample product on moist skin, T72 represents the viscosity of institute's test sample product in dryness or moist skin after 72 hours, and T168 represents the viscosity of institute's test sample product in dryness or moist skin after 168 hours.
As can be seen from Figure 3, when T0, the viscosity of above institute's test sample product to skin is all greater than 40g/inch.HPA-12/12L, the initial viscosity of HPA-14/14L in dry skin is 90-110g/inch, preferably ~ 100g/inch, initial viscosity on moist skin is 30-50g/inch, preferably ~ 45g/inch, the viscosity in dryness or moist skin after 72 hours is 160-190g/inch, preferably ~ 170g/inch, viscosity in dryness or moist skin after 168 hours is 100-120g/inch, preferably ~ 110g/inch.When T72 and T168, with commercial samples Tegaderm std, Tegaderm HP, IV-3000 compares, HPA-12L and HPA-14L has similar viscosity, and its viscosity is higher than reference sample MMD, illustrates that above two kinds of formulas have and good holds viscosity.HPA-12 and HPA-14 then has similar viscosity to MMD, but they when T72 and T168 viscosity lower than with commercial samples Tegaderm std, Tegaderm HP, IV-3000.
Except viscosity, cull and crimping are also the important factors affecting dressing use properties.0-5 is adopted to evaluate cull, the crimping of dressing in the present invention.0 is divided into without cull or crimping, increases progressively successively, and 5 are divided into whole cull or sample to drop.
Assess the cull of sample when T72 and crimping as shown in Table 6.Cull evaluation result as can be seen from table six, the formula HPA-12L in the present invention, HPA-14L, HPA-12 and HPA-14 all do not observe cull in inner clinical experiment, have obvious advantage than commercially available prod Tegaderm HP and IV-3000.
Crimping evaluation result as can be seen from table six, in the 72h of assessment, assess sample and all do not occur coming off.HPA-12L and HPA-14L does not observe crimping at T72 or only has slight crimping, and with commercially available prod Tegaderm HP, Tegaderm Std and IV-3000 is identical.The crimping situation of HPA-12 and HPA-14 is serious than above-mentioned sample, but its assessment result is still better than MMD.
Assess the cull of sample when T1682 and crimping evaluation result as shown in Table 7.Cull evaluation result as can be seen from table seven, formula HPA-12L in the present invention, HPA-14L, HPA-12 and HPA-14 all do not observe cull in the i.e. inside clinical experiment of 7 days that reaches 168h, have obvious advantage than commercially available prod Tegaderm HP and IV-3000.
As can be seen from the crimping evaluation result of table seven, to commercially available prod Tegaderm HP and IV-3000, there is similar hemming performance reaching (T168) HPA-12L and HPA-14L in the test of 7 days, all have a sample or two samples to come off.Than above-mentioned sample seriously, there is coming off of 3-4 sample in the crimping of HPA-12 and HPA-14 and dropping situations.
The inside clinical test results of table six T72 cull and crimping
The inside clinical test results of table seven T168 cull and crimping
Fill a prescription in comprehensive assessment the present invention in the performance of each time point, can find out that HPA-12L and HPA-14L has better viscosity, less cull than HPA-12 and HPA-14, better hemming performance.And HPA-12L and HPA-14L has higher MVTR than HPA-12 and HPA-14.Therefore, suitable to more saturating vapour, the dressing of a new generation that cull is less, adhesive tape product.
In sum, the present invention discloses one and there is high vapour permeability (MVTR ~ 1900g/m simultaneously
2/ 24hrs), high viscosity (within 7 days, do not come off, not crimping, peeling force has 100g/inch), the pressure sensitive adhesive of low irritant.It is formed primarily of four class monomers, the hydrophilic acrylate monomer of hydroxyl or oxyethyl group, short chain with hydrophobic acrylic acid's ester class soft monomer of long-chain and the propylene class hard monomer of band polar group.This pressure sensitive adhesive shows in human test compares the huge advantage of market like product in performance, is the first-selection of medical dressing of future generation.Need the industrial adhesive field of high water vapor transmittance at other, as electron trade also can hold out broad prospects simultaneously.
Claims (21)
1. a pressure-sensitive acrylate, described pressure sensitive adhesive to comprise by following monomer by the free-radical polymerized polymkeric substance formed:
A) hydrophilic acrylate monomer of the hydroxyl or oxyethyl group of .10%-30%, in the gross weight of all monomers by 100%;
B) hydrophobic acrylic acid's esters monomer of the short chain of .50%-70%, in the gross weight of all monomers by 100%; The structural formula of hydrophobic acrylic acid's esters monomer of described short chain is CH
2=CHCOOR
1, R
1it is the alkyl containing 1-5 carbon atom;
C) hydrophobic acrylic acid's esters monomer of the long-chain of .10%-35%, in the gross weight of all monomers by 100%; The structural formula of hydrophobic acrylic acid's esters monomer of described long-chain is CH
2=CHCOOR
2, R
2it is the alkyl containing 6-14 carbon atom;
D) .0.5%-5% can with third vinyl monomer with polar group of above-mentioned monomer a-c copolymerization, in the gross weight of all monomers by 100%.
2. pressure-sensitive acrylate according to claim 1, the wherein said ratio of hydrophilic acrylate monomer shared by the gross weight of all monomers that be hydroxyl or oxyethyl group is 15%-25%.
3. pressure-sensitive acrylate according to claim 1, the ratio that hydrophobic acrylic acid's esters monomer of wherein said short chain is shared in the gross weight of all monomers is 55%-65%.
4. pressure-sensitive acrylate according to claim 1, the ratio that hydrophobic acrylic acid's esters monomer of wherein said long-chain is shared in the gross weight of all monomers is 20%-30%.
5. pressure-sensitive acrylate according to claim 1, wherein said can the ratio shared in the gross weight of all monomers with the third vinyl monomer of monomer a-c copolymerization be 1%-3%.
6. pressure-sensitive acrylate according to claim 1, wherein said acrylic ester monomer that is hydroxyl or oxyethyl group is selected from following one or more: 2-(2-ethoxy ethoxy) ethyl propylene acid esters, Hydroxyethyl acrylate, vinylformic acid 4-hydroxyl benzyl ester.
7. pressure-sensitive acrylate according to claim 1, hydrophobic acrylic acid's esters monomer of wherein said short chain is selected from following one or more: methyl acrylate, ethyl propenoate, butyl acrylate.
8. pressure-sensitive acrylate according to claim 1, hydrophobic acrylic acid's esters monomer of wherein said long-chain is selected from following one or more: ethyl acrylate, Isooctyl acrylate monomer.
9. pressure-sensitive acrylate according to claim 1, wherein said third vinyl monomer is selected from third vinyl monomer with carboxyl or amide group.
10. pressure-sensitive acrylate according to claim 9, wherein said third vinyl monomer with carboxyl or amide group is selected from following one or more: acrylamide, vinylformic acid, Methacrylamide, methacrylic acid.
The Pressuresensitive Tape of 11. 1 kinds of high vapour permeabilities, it comprises the one deck be coated on backing pressure-sensitive acrylate according to claim 1, described Pressuresensitive Tape is in positive agar diffusion method test, and the water vapor transmittance that the dry glue that 20.3 microns of polyurethane films are coated with one deck 25 microns records can reach 1900g/m
2/ 24hrs/37 DEG C.
12. Pressuresensitive Tapes according to claim 11, wherein said backing is polyurethane film.
13. 1 kinds of methods preparing Pressuresensitive Tape according to claim 11, described method is included on backing and is coated with one deck pressure-sensitive acrylate according to claim 1, and solidifies by making pressure-sensitive acrylate crosslinked.
14. methods according to claim 13, wherein said crosslinked by realizing with radiation exposure or interpolation linking agent.
15. methods according to claim 14, wherein said linking agent is selected from following one or more: isocyanate crosslinking, aziridine crosslinker, metallic-ion crosslinking agent; The content of described linking agent accounts for the 0.01%-5% of the weight of total monomer.
16. methods according to claim 14, wherein said ray is gamma ray.
17. 1 kinds of medical dressing, it comprises Pressuresensitive Tape according to claim 11, and encloses one deck release film on the glue face of described Pressuresensitive Tape.
18. medical dressing according to claim 17, wherein said release film is made up of the cated base material of tool, and described base material is selected from following one or more: stationery base material, film class base material, aluminium foil class base material, polyolefin based materials base material.
19. medical dressing according to claim 18, wherein said coating is containing one or several following compounds: organosilicon, fluorochemical, fluorine-silicon copolymer thing, side chain are the polyolefinic compound of long-chain.
20. medical dressing according to claim 17, its initial viscosity in dry skin is 90-110g/inch, initial viscosity on moist skin is 30-50g/inch, viscosity in dryness or moist skin after 72 hours is 160-190g/inch, and the viscosity in dryness or moist skin after 168 hours is 100-120g/inch.
21. medical dressing according to claim 20, its initial viscosity in dry skin is ~ 100g/inch, initial viscosity on moist skin is ~ 45g/inch, viscosity in dryness or moist skin after 72 hours is ~ 170g/inch, viscosity in dryness or moist skin after 168 hours is ~ 110g/inch, wherein ~ represent mean value.
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| CN201110388243.3A CN102719205B (en) | 2011-11-29 | 2011-11-29 | Pressure-sensitive adhesive, pressure-sensitive adhesive tape, preparation method of the pressure-sensitive adhesive tape and medical dressing |
| PCT/US2012/066956 WO2013082222A1 (en) | 2011-11-29 | 2012-11-29 | A pressure sensitive adhesive |
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| CN102719205B true CN102719205B (en) | 2015-02-18 |
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| CN103865443B (en) * | 2012-12-07 | 2016-08-24 | 上海华谊丙烯酸有限公司 | Transfevent binding agent and preparation method thereof |
| CN105288812A (en) * | 2015-11-13 | 2016-02-03 | 合肥美迪普医疗卫生用品有限公司 | Trachea cannula fixing device |
| CN105885741A (en) * | 2016-05-17 | 2016-08-24 | 上海巍盛化工科技有限公司 | Medical pressure-sensitive adhesive and medical dressing |
| CN107163866B (en) * | 2017-05-27 | 2020-09-15 | 江苏理工学院 | Medical ultraviolet-curing water-based conductive pressure-sensitive adhesive |
| JP2019014852A (en) * | 2017-07-10 | 2019-01-31 | 日本合成化学工業株式会社 | Adhesive composition, adhesive and adhesive sheet |
| CN109589445A (en) * | 2018-12-05 | 2019-04-09 | 广东高璐美数码科技有限公司 | A kind of improved aqueous medical pressure sensitive adhesive band of antiperspirant and preparation method thereof |
| CN112107720A (en) * | 2020-09-18 | 2020-12-22 | 华熙生物科技股份有限公司 | Medical pressure-sensitive adhesive with good air permeability and application of ectoin in improving air permeability of medical pressure-sensitive adhesive |
| CN115820199B (en) * | 2022-12-09 | 2024-05-03 | 浙江工业大学 | Modified black talcum antibacterial conductive pressure-sensitive adhesive, medical electrode slice and preparation method thereof |
| CN115779156A (en) * | 2022-12-16 | 2023-03-14 | 振德医疗用品股份有限公司 | Deiodination viscose composition and operation film thereof |
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