CN101052475B

CN101052475B - Silicone urine-collecting cover with integral adhesive

Info

Publication number: CN101052475B
Application number: CN2005800339448A
Authority: CN
Inventors: H·L·尼尔森
Original assignee: Coloplast AS
Current assignee: Coloplast AS
Priority date: 2004-09-06
Filing date: 2005-09-05
Publication date: 2012-08-29
Anticipated expiration: 2025-09-05
Also published as: JP4796065B2; DE602005027224D1; ATE503589T1; JP2008512222A; CN101052475A

Abstract

Using an oxidative process it is made possible to apply an adhesive material to silicone. The process is controlled, allowing selective oxidative treatment to a silicone structure enabling treatment to the inside of a tubular structure.

Description

Silicone urine-collecting cover with integral adhesive

Technical field

The present invention relates to through using all or optionally oxidation corona, plasma, flame treatment; Or ultraviolet ray, electron beam or γ radiation; Or chemical oxidation treatment, or use the silicone binder course that pressure-sensitive surgical appliance adhesive only is connected the partially or completely inboard of the unprocessed silicone urine-collecting cover (urisheath) of sulfuration, or the elastomer of other sulfuration or the undressed urine of thermoplastic elastomer (TPE) put.

Background technology

External urinary catheter is generally used for the urinary catheter device, and this urinary catheter device helps male uracratia and in hospital, is used for the situation relevant with operation with the treatment of urethral disease.This external urinary catheter generally includes sheath or the body part (like tubular body) that surrounds cloudy stipe part and is provided with the tip portion of relatively shorter delivery pipe; This delivery pipe is connected on the urine collecting bag through flexible pipe, and this urine collecting bag for example is fixed on user's the bed or shank.

As a rule, external urinary catheter is transmitted at roll-up state.Under this delivery status, jacket portions is rolls-up onto a kind of degree with a plurality of continuous coiling portions, and promptly adhesive phase is contained in the coiling portion fully, thereby allows the urine cover is packed and handled, and the inboard of jacket portions is sticked on the surrounding environment.For external urinary catheter is used on penis, jacket portions is launched slightly, till the adhesive phase on the inboard of jacket portions comes out.In this state, external urinary catheter is placed on the penis, thereby adhesive phase touches skin, and the remainder of jacket portions launches subsequently.

Silicone is considered to have the superperformance of making the urine cover.The subject matter of using silicone is the inboard that adhesive is securely sticked to the urine cover, and the user can easily launch the urine cover simultaneously.Considered adhesive is sticked on the ready-made unprocessed silicone urine-collecting cover very difficulty, this is because silicone material itself is releasable material to all other contact adhesives except silicone adhesive agent.

US5176666 has described and how contact adhesive has been sticked to silicone impregnated urine and put.This is to carry out through unvulcanized silicone urine-collecting cover being immersed on the dipping axle, and wherein, on the dipping axle, adhesive has been applied to suitable length, and it is peelled off, and on axle, with adhesive silicone is vulcanized then.At least can guarantee between silicone and adhesive that like this physics is bonding.

US5779964 has described how contact adhesive is sticked to the silicone impregnated urine cover that has vulcanized.This through adhesive is applied to the urine cover outside, then to its sulfuration, then the surface preparation layer is applied to the top and carries out, this surface preparation layer is stronger to the affinity of silicone rubber to the affinity specific viscosity mixture of silicone rubber.Roll through urinating cover, make the interior side contacts of surface preparation layer and silicone urine-collecting cover, thus adhesive is transferred to the inboard that urine overlaps with the surface preparation layer.

Silicone adhesive agent can adhere to ready-made unprocessed silicone urine-collecting cover; But brought the problem that need place specific releasing layer in the outside of urine cover, placing specific releasing layer is in order to make silicone pressure-sensitive adhesive can not stick to the outside of urine cover at roll-up state.

Use all other normally used pressure-sensitive surgical appliance adhesives, can make the silicone material through over cure that contact adhesive is produced releasing effect, make when after using, taking away product, adhesive sticks on the skin rather than sticks to urine and puts.Use these adhesives, can make adhesive firmly stick to a side (inboard) of silicone urine-collecting cover usually and do not stick to opposite side (outside).

Need other a kind of mode that normally used pressure-sensitive surgical appliance adhesive is sticked on the unprocessed silicone urine-collecting cover that partially or completely vulcanized.

Summary of the invention

Be amazingly, only have been found that after a side of the silicone that partially or completely vulcanized is carried out optionally corona or plasma treatment that can make multiple pressure-sensitive surgical appliance adhesive stick to urine and put, the opposite side at silicone keeps release characteristics simultaneously.If this release characteristics can not keep fully, for example, because product is very thin, or the physical characteristic of silicone and/or bonding composition, cover outward around section thereby can adhere to extra layer of silicone, this is outer to cover adhesive area around section.

The specific embodiment

Therefore, the present invention relates to a kind of jointing material preferably is applied to the method on the silicone elastomer, this method comprises:

(a) elastomer is applied oxidizing process,

(b) adhesive is applied on the elastomer.

Use the urine cover as example, for example the technical scheme of the corona treatment of urine cover can be handled in the inboard rather than the outside of urine cover.This carries out through following steps: corona discharge electrode is placed in the urine cover and in the zone that will handle it is moved along length that urine overlaps; Preferably do not touch the surface, provide simultaneously to handle and urinate the cover inboard and do not handle the enough power in the outside.Through this corona discharge; Existing unvulcanized low molecule silicone oil is removed from inner surface; Form polar group for example-OH and-COOH; Said polar group can make surface tension from being increased to 30-60dyn/cm below the 23dyn/cm, thereby might be to multiple different adhesive, for example all normally used pressure-sensitive surgical appliance adhesives (comprising acrylic acid PSA ' s) become wet and thus physical adherence to the surface.If necessary, formed-OH also might covalently stick to adhesive on the silicone with-COOH polar group.This selectable corona treatment also can be carried out by enough other possible urine cover materials.

Preferably, in a kind of structure, form elastomer usually, this structure example is as being the cylinder that is used for jacket portions or whole urinary catheter (urine cover).

In one embodiment, this elastomer is the chemical crosslinking elastomeric material, for example natural rubber, acrylonitrile-butadiene rubber, chloroprene rubber, SBS rubber or other synthetic lattice, silicone, polyurethane dispersion or latex.This crosslinked heat, ultraviolet light or electron beam of can passing through produces.In another kind of embodiment; Elastomer is a thermoplastic elastic material, and for example styrenic elastomer block copolymer (for example SEBS, SBS, SIS, SIBS) or thermoplastic polyurethane (for example Estane), polyether ester (polyetherester) (like Hytrel), polyetheramides (like Pebax), polypropylene/EPDM (like Santoprene) have the homopolymer polypropylene or the copolymer (Versaflex (E of the one-tenth piece tacticity of control _XXON) or Versify (Dow Chemical)).In a preferred embodiment, this elastomer is the silicone that partly or entirely vulcanizes.

In this article, silicone material is meant polymeric material, and it contains silicon in the polymer main component.Usually, the polymer main component mainly comprises polysiloxanes-O-Si-.In many cases, silicone material mainly comprises dimethyl silicone polymer (PDMS), but also can use phenyl and other to contain the carbon of side group.

Multiple different sulfuration (sclerosis) chemistry can be used for silicone.Main kind is for adding sulfuration, concentrated sulfuration, free radical curing, moisture sulfuration (RTV), ultraviolet ray sulfuration and electron beam vulcanization.

In adding sulfuration, contain vinyl (H2C=CH-) or other thiazolinyl group and use the crosslinking agent sulfuration that contains the SiH base as the polysiloxanes of end group or side group.Usually with the rhodium or the platinum that contain catalyst catalysis is carried out in this reaction.This specific system SiH base also can be positioned on the siloxanes main component, uses thiazolinyl or the vinyl that contains crosslinking agent then.

In concentrating sulfuration, contain the basic polysiloxanes of OH with the sulfuration of SiH crosslinking agent, with the tin that contains catalyst catalysis is carried out in this reaction usually, use the specific accelerator that is coated with amine usually.

The moisture silicon sulfide ketone is also referred to as rtv silicone (room temperature vulcanization silicone), and it vulcanizes with the substitution reaction that has water (H2O) usually, and produces acetate.

In free radical curing, vulcanize as the polysiloxanes of end group or side group containing vinyl (H2C=CH-) or other thiazolinyl group with peroxide cross-linking agent.

In ultraviolet ray sulfuration and electron beam vulcanization; Vulcanize as the polysiloxanes of end group or side group containing acrylates with ultraviolet ray or electron beam irradiation, this ultraviolet ray or electron beam irradiation use optics or the electron beam initator causes this process and to its acceleration.The epoxy silicone also can use with cationic initiator.

For moulded product in the mould of sealing, the preferred use added silicon sulfide ketone, and this is because it can only vulcanize through heat; And can not emit any gas; For example H2, H2O or contain the product of low molecular carbon perhaps need any gas that is used to vulcanize, for example H2O.In the preferred embodiment of the present invention, silicone is injection-molded and forms.In relevant preferred embodiment, silicone is an injection mould antidiuresis cover.

For the silicone release coat, use multiple sulfuration type usually, comprise and add sulfuration, concentrated sulfuration, ultraviolet ray and electron beam vulcanization.

Jointing material is arranged on the silicone sheath.Make the adhesion that holds them in together increase through corona treatment disclosed herein.This is because the surface polarity that too much increases produces, and this polarity is through volatile silicone oil is removed from the surface, and oxidation should obtain on the surface.Except polar forces, some acryloid cement also can react in sulfuration with-COOH base with-OH, produces covalent bond.Yet, when sheath is rolled, adhesive will with other side contacts of silicone sheath.So requirement is removed adhesive from other side of silicone sheath power is lower.This handles and can guarantee the surface through optionally being avoided, thereby keeps nonpolar at its nonpolar state.In use, the adhesive of expansion will contact with skin.It is peel value that adhesive is removed required power from skin.Preferably, the peel value of adhesive less than to the adhesion of silicone sheath to avoid making adhesive residue on skin.

Through above-mentioned method; Might use multiple known surgical appliance adhesive; For example, they are firmly sticked on the unprocessed silicone urine-collecting cover based on the adhesive of acrylic resin, polyvinylether, polyurethane, polyvinylpyrrolidone, SIS, PIB or rubber.It can contain solvent, water base or hot melt, and finally vulcanizes through heat, ultraviolet ray or electron beam irradiation.The polarity pressure sensitive adhesive materials is as being preferred based on acrylic resin, polyethers, polyvinylether, polyurethane, polyvinylpyrrolidone.In a preferred embodiment, jointing material is an acrylic pressure-sensitive adhesive.

Other adhesive that is used for pressure-sensitive surgical appliance adhesive that styrenic elastomer or polyisobutenyl hot-melt adhesive right and wrong are usually seen.In another embodiment, use the polyvinylether based adhesive that contains solvent.

In an embodiment of the present invention, use silicone PSA, use fluorosilicone (flouro silicone) or other then with respect to the releasable material of silicone PSA whole releasing layer as the outside as surgical appliance adhesive.

In another kind of embodiment, silicone PSA is a surgical appliance adhesive, and independent film release liner is wound between the layer in the coiling portion.This release liner is for example processed by polyolefin (poleolefin) thermoplastic film material.

Usually, silicone structure complete cure.Yet this need not carry out oxidizing thermal treatment.Therefore, in another embodiment, with the silicone structure partial vulcanization.

A special advantage of the present invention is for can only being applied to adhesive on the appointed area., oxidizing thermal treatment realizes this point when optionally being applied to the selected part of product.Under the situation of urine cover, oxidizing thermal treatment optionally is applied to the inboard of silicone external urinary catheter.Thus, can under the situation of the release characteristics on the outside of not damaging external urinary catheter, carry out this process.

Silicone uses on multiple product.In order to realize the object of the invention, preferably, the silicone product uses as medical product.That is, for example from the group that comprises urinary catheter, plaster, bandage, outer breast prosthesis and external urinary catheter, select.

A special problem is that this patent confirms and solved how pressure-sensitive surgical appliance adhesive is bonded on the unprocessed silicone urine-collecting cover of complete cure, and makes complete acting urine cover simultaneously.Accordingly, in a preferred embodiment, silicone structure is the urine cover.Should be appreciated that through this term " complete cure " this product is stable and for example be applicable in the medical treatment device on certain size.Yet, still exist the unvulcanized silicone oil of certain percentage, be typically about 1-5%.

Can apply the different oxidation process.The processing or the oxidizing thermal treatment of the material that this oxidizing process is for example carried out for the chemical treatment of material, through ultraviolet ray, electron beam (known β ray) or gamma radiation.

Exist multiple oxidizing thermal treatment.In one embodiment, oxidizing thermal treatment is a corona treatment.In another embodiment, oxidizing thermal treatment is a plasma treatment, for example uses the plasma pen.In the 3rd embodiment, oxidizing thermal treatment is a flame treatment, for example through using oxidizing flame.

The specific selection of oxidation processes depend on the material of use be silicone or above-mentioned any other possibly be used for the material of the jacket portions of urinary catheter.

Exist and how but adhesive is applied to the system of selection on the silicone structure.In one embodiment, through described silicone structure being placed on the top of adhesive layer, at once said silicone structure being removed afterwards, adhesive is applied to through on the silicone structure of oxidizing thermal treatment.In a kind of certain embodiments, this applies is through carrying out on the top that is wound on the axle that has adhesive.In another embodiment, after being wound on silicone structure on the axle, the bilateral band application is added on the axle.When rolling once more, the purpose in order to store is placed on adhesive on the silicone structure.

Another technical scheme relates to jointing material is applied to the structural method of silicon sulfide ketone, and this structure comprises the vulcanizing adhesive that bonds together through silicone adhesive layer.In this embodiment, guarantee through tack coat bonding.

Other or the scheme that makes up can be used a kind of special tack coat.Preferably, this tack coat is essentially layer of silicone.This sticky object can be liquid, the solvent that is provided or emulsion silicone; It is based on one or more parts; And vulcanize through adding reaction or concentration response, said interpolation reaction or concentration response use heat, moisture, ultraviolet ray, electron beam or other means.Tack coat also can be the silicone adhesive agent that has vulcanized with PSA characteristic.This tack coat also can comprise additive; For example titanate, zirconates or silane (having or do not have other for example effect of acrylic acid, amine, epoxy root) are so that guarantee lip-deep arbitrary surface or the two lip-deep bondings at PSA and unprocessed silicone urine-collecting cover, and the surface of PSA surface and unprocessed silicone urine-collecting cover will bond together.Preferably, undressed urine cover is processed by the silicon sulfide ketone material.

In one aspect of the invention, between the bonding of adhesive, increase cleaning.Thus, will remove the vestige of unvulcanized low molecule silicone residue.In the example of urine cover, cleaned the inboard of silicone structure at least.Clean method comprises that carbon dioxide cleans or carbon dioxide dry ice cleans (ice blasting).

The corona treatment that it has been generally acknowledged that silicone elastomer has very short effect, and this is because the unvulcanized silicone oil of a small amount of (1-5%) is always stayed in the product after sulfuration.Through preliminary treatment urine cover under 200 ℃ the temperature in heating furnace 5 minutes, just can obtain following advantage from least some silicone oils of surface evaporation:

1. the better result of corona treatment, and corona treatment and apply between the adhesive possible longer during.

2. urinating lower silicone oil content on the outer surface that overlaps.This just means when the urine cover is rolled, and is of reduced contamination by silicone oil on the adhesive surface

Under this mode, before using the urine cover, can access good result after storing 3 days rolling with winding position not.

Should be noted that; Longer evaporation periods (for example 200 ℃ following 1 hour) is final to be produced the more of surface more and pollutes; This is because the non-volatile silicone oil of higher molecular and the low molecular weight volatile silicone oil that is produced and nonvolatile silicone oil of in the longer volatilization cycle, forming from the teeth outwards will be transferred on the said surface.

In addition, be appreciated that the present invention has disclosed the tubular body of being processed by elastomer; Wherein, At least oxidation is arranged on the inboard of tubular body around section in elastomeric, and oxidation is elastomeric is arranged on the outside of tubular body around section outward, in not being covered with at least around section outward around section.

Through providing oxidation elastomeric interior, can easily other materials be connected on the tubular body around section.

In one embodiment, tubular body is the urine cover, is used for can advantageously sticking to the adhesive that the urine cover is bonded on the skin interior around section.

In one embodiment, interiorly form by tubular body around section.In for example can be through the inner segment oxidation be formed by body around section.For example can carry out through oxidation processes described herein, oxidation processes is corona treatment, plasma treatment or flame treatment for example.

In another embodiment, should interior be applied on the tubular body around section.For example, this applies this layer through axle and carries out, and on axle, is provided with the elastomer of oxidation.Then this tubular body is wound on the axle, thus, with the elastomer transfer of oxidation in be provided with on the inboard around the tubular body of section.Utilize known acrylic acid locking, the elastomer of oxidation will automatically be connected on the tubular body.Acrylic acid locking is a kind of known phenomena for the acryloid cement that on silicone material, (for example, is generally the silicone that scribbles release liner).

Usually it produces through unvulcanized silicone.Sulfuration and SiH base good in the addition curing silicone resin can guarantee usually that with the basic low ratio of H2C=CH-acrylic acid locking can not take place.Yet; Except the locking to the SiH base of fine description, the locking to H2C=CH-base and Si-OH base is proposed also in document (J.L.Keddie: " Evidence from infrared Ellipsometry for Covalent Bonding at aPolymer/Polymer interface with Relevance to " Lock-Up " inPressure-Sensitive Adhesive Laminates ").The acrylic acid locking that is used for liner has also been described, its in oxidation environment through electron beam treatment, yet, do not produce any locking problem (US6780484) in the electron beam treatment of hypoxemia level (less than 10ppm).

Advantageously, form by tubular body around section outward.For example in providing, can realize during around section through corona treatment.Through applying corona treatment time of one section control only, only can realize in tubular body top is provided with around section.Therefore, the non-corona treatment through tubular body partly is provided with outer around section.

Alternatively, as stated,, can advantageously be provided with outer around section through tubular body through being applied on the tubular body around section with interior.

In another embodiment, will be applied on the tubular body around section outward.For example, this can carry out during fully through tubular body in inner section.Thus can with elastomer for example silicone as applying around section outward, as stated.

Outer through applying around section according to above-mentioned any method, can be outside around section during as releasing layer, the urine cover expansion that will reel easily, said urine cover has and is coated with the interior around section of adhesive.The silicone sheath of good sulfuration has the appropriate balance of SiH and CH2=CH-base; It can guarantee to realize this point; Or finally apply by discharging the additional layer that silicone coating forms; It is looped around the outside, so that obtain best release characteristics, this dual mode is after also being to be used in acceleration or delaying aging at first.

The advantage that the oxidation internal layer is provided is that other materials can be fixed on the elastomer thus.Therefore, it is elastomeric interior around section that adhesive for example can be arranged on generation, and said adhesive will stick on other surfaces, for example can stick to the urine cover on the skin.

Description of drawings

Fig. 1: circular electrode

Fig. 1 illustrates first embodiment according to corona electrode 1 of the present invention.This electrode is by first circular aluminium electrode tip 2, the one PE (polyethylene) dish 3 and first steel pole 4.

Make the electrode tip charging produce the corona that is used for corona treatment.This will produce capacity effect.Along with the increase of electric charge, the gas ionization around the electrode tip also finally can conduct electricity, and produces corona thus.When common containing carried out corona treatment in the oxygen air, produce ozone and free radical, it will produce chemical reaction with said surface subsequently.The same energy that is produced is removed volatile contaminant from said surface.This for example will make with get wet surface and finally it to be produced covalent bond easier of adhesive.

The PE dish is as the insulator setting.It helps to control the border of corona, thereby can send corona at controllable segment.

Fig. 2: the circular electrode in the operation

See that in sectional view Fig. 2 illustrates the corona electrode 1 that inserts in the urine cover 5.In processing procedure, corona electrode is longitudinally transferred in the urine cover.

Fig. 3 and 4: improved circular electrode

Fig. 3 and 4 shows second embodiment that is arranged on the corona electrode 10 in the second urine cover 11.Fig. 4 shows the sectional view of cutting open along the IV-IV among Fig. 3.

In this embodiment, the second corona electrode head 12 and the 2nd PE dish 13 closely is provided with than first embodiment of corona electrode 1 more each other.Use when operating at the second corona electrode head like this with the first corona electrode head, 2 identical parameters, provide littler, but the corona of more concentrating.

Through shown in Fig. 1-4 and the corona treatment of carrying out of description before, the urine cover can advantageously be handled after production.Advantageously, this for example will make adhesive be applied in urine and put, and no matter the method for producing this urine cover how.

It is molded that this just makes the urine cover be blow molded, and for example this just allows to put formation rib 15 at urine.This rib for example can not put formation at urine in the molded process of dipping.

Fig. 5,6 and 7: oxidation panel

Fig. 5-7 with section how to illustrate with interior around section be provided at the different embodiment on the tubular sheath around section outward.

Fig. 5 illustrates a section of the wall 20 of tubular sheath.In this embodiment, in the interior wall 20 that is formed on tubular sheath around section 21 parts.This can for example form through the corona treatment that on tubular sheath, applies limiting time.Be provided with so outer around the part of section 22 as tubular wall, in it covers around section and be not exposed under the corona treatment.

Fig. 6 illustrates a section of the wall 20 of tubular sheath, the interior wall 20 that has formed tubular sheath around section 23 run through part.Outward around section 24 with after-applied, be covered with in around section.Wall 20 identical materials around the Duan Youyu tubular sheath form outward.

Be applied on the urine cover inboard as additional layer around section in Fig. 7.This can realize through for example on axle, applying around layer of silicone.This layer was oxidized after urine cover was wound on the axle, and because acrylic acid locking, this layer be transferred to urine put with in providing around section 25, become the part of tubular wall 20 outside being appreciated that around section 26, and covering is interior around section.

Advantageously, interior the putting at urine around the section permission of oxidation connects/provides material different.Adhesive phase for example can be applied to interior around on the section.

Provide the oxidized for example interior process of elastomer in following example, to be understood around section.

Example

Example 1A: corona discharge optionally

Undressed urine cover is obtained by Dow Corning C6-540 silicone elastomer.Then 200 ℃ of following heat treatments 5 minutes, to evaporate not silicon sulfide ketone of low molecule.

Corona treatment is carried out with circular electrode in the inboard of the urine cover of diameter 30mm, and the voltage of electrode is 40.000V, and power is 120W.The electrode of diameter 24mm moved to the other end from the inboard end of the jacket portions of product in 2 seconds, through the distance of 80mm.Through diameter is the polyethylene pan of 28mm, can mechanically guarantee from the electrode edge to the inner surface 2 to 4mm apart from (see figure 1).

By this way, have only the inboard of urine cover to be processed, show as the surface tension more than 35dyn/cm on the inboard, the surface tension below 28dyn/cm on the outside.Use is higher than the power of 150W, and perhaps electrode can or all be seen unwanted raised surface tension force on the position in some position in the outside, thereby damage the release characteristics of on the outside, wanting near to or in contact with the inboard.

Top in the aluminium axle that scribbles suitable silicone release coat applies acrylic pressure-sensitive adhesive, is the Gelva2853 from UCB-Solutia in this case.Adhesive is dry and vulcanized 5 minutes in the heating furnace of 200 ℃ (effective temperature is 130 ℃).After being cooled to 50 ℃, be wound on the axle through the unprocessed silicone urine-collecting cover of corona treatment.Immediately with its expansion.Thus adhesive is transferred to the inboard of urine cover from axle.

After keeping 24 hours under 40 ℃.Peel value at room temperature is identical level (7N) for being used in the identical adhesive that natural emulsion urine puts, and does not have adhesive residue.Expansion value lower and more stable (2N).

Example 1B: corona discharge optionally

Obtain undressed urine cover by silicone elastomer Dow Corning C6-540.Corona treatment is carried out with circular electrode in the inboard of the urine of diameter 30mm cover, and the voltage of this circular electrode is 40.000V, and power is 80W.The electrode of 24mm diameter is moved to the other end with the speed of 1000mm/sec from the inboard end of product jacket portions, through the distance of 80mm.Through diameter is the thin dish of polyethylene of 28mm, can mechanically guarantee from the electrode edge to the inner surface 2 to 4mm apart from (see figure 1).By this way, have only the inboard of urine cover to be processed, show as the surface tension more than 32dyn/cm on the inboard, the surface tension below 28dyn/cm on the outside.Top in the aluminium axle that scribbles suitable silicone release coat applies acrylic pressure-sensitive adhesive, is the Gelva2853 from UCB-Solutia in this case.Adhesive is dry and vulcanized 45 seconds in infrared furnace, and the temperature of the heating element heater of infrared furnace is 480 ℃, and the effective temperature that provides is 110 ℃.After being cooled to 50 ℃, be wound on the axle through the unprocessed silicone urine-collecting cover of corona treatment.Immediately with its expansion.Thus adhesive is transferred to the inboard of urine cover from axle.After keeping 24 hours under 23 ℃.Peel value at room temperature is identical level (7N) for being used in the identical adhesive that natural emulsion urine puts, and does not have adhesive residue.Expansion value lower and more stable (< 2N).

Example 1C: selectivity corona discharge with extra releasing layer

The process preparation of corona treatment urine cover to describe among the embodiment 1B.Urinating after cover is placed on the step on the axle that scribbles adhesive, apply special interpolation sulfuration through roller and discharge the silicone thin layer.Silicone vulcanized in infrared furnace 90 seconds, and the temperature of the heating element heater of infrared furnace is 450 ℃, and the effective temperature that provides is 150 ℃.After being cooled to below 50 ℃, will urinate cover and roll from axle, thus adhesive is transferred to the inboard of urine cover from axle.After keeping 24 hours under 23 ℃.Peel value at room temperature is identical level (7N) for being used in the identical adhesive that natural emulsion urine puts, and does not have adhesive residue.Expansion value lower and more stable than among the example 1B when 40 ℃ and 60 ℃ of following accelerated ageings.

Embodiment 1D: the selectivity corona discharge on other silicone material

By obtaining undressed urine cover among silicone elastomer Dow Corning C6-540, Dow Corning C6-530, GE-Bayer LSR4040 and the Wacker3003/40.Some parts in the urine cover was 200 ℃ of following after cure 1 hour.Corona treatment is carried out with circular electrode in the inboard of the urine of diameter 30mm cover, and the voltage of this circular electrode is 40.000V, and power is 90W.The electrode of 24mm diameter is moved to the other end with the speed of 1000mm/min from the inboard end of product jacket portions, through the distance of 80mm.Through diameter is the thin dish of PE of 28mm, can mechanically guarantee from the electrode edge to the inner surface 2 to 4mm apart from (see figure 1).By this way, have only the inboard of urine cover to be processed, show as the surface tension more than 34dyn/cm on the inboard, on the outside, be lower than the surface tension of 28dyn/cm.Applying acrylic pressure-sensitive adhesive scribbling on the aluminium axle top of suitable silicone release coat, is the Gelva2853 from UCB-Solutia in this case.Adhesive is dry and vulcanized 45 seconds in infrared furnace, and the temperature of the heating element heater of infrared furnace is 470 ℃, and the effective temperature that provides is 110 ℃.Be cooled to after 50 ℃, will passing through the unprocessed silicone urine-collecting cover of corona treatment and roll from axle.In infrared furnace, will urinate cover sulfuration 90 seconds in addition, the heating element heater of infrared furnace is 480 ℃.The effective temperature that in the axle of using, provides is 120 ℃.After being cooled to below 50 ℃, will urinate cover and roll from axle, thus adhesive is transferred to the inboard of urine cover from axle.After 60 ℃ of down aging 1 weeks, have only with Dow CorningC6-540 and process and can be unfolded at 200 ℃ of urine covers that do not have to vulcanize in following 1 hour.All all can not be unfolded through after cure or without other sample that after cure is processed.If yet picture uses extra release coat in example 1C, all these materials all are suitable for using.

Example 2: selectivity corona discharge

Unprocessed urine cover and the preliminary treatment of carrying out through evaporation and corona discharge are according to accomplishing with example 1 identical mode.Apply the preliminary treatment silicone at the top of the aluminium axle that scribbles suitable silicone release coat and process the urine cover.Top at the silicone sheath applies acrylic pressure-sensitive adhesive, is the Gelva2853 from UCB-Solutia in this case.Adhesive is dry and vulcanized 5 minutes in the heating furnace of 200 ℃ (effective temperature is 130 ℃).Behind cool to room temperature, corona urine cover is rolled from axle.When launching the urine cover, adhesive is transferred to the inboard of urine cover safely.Under 40 ℃ through 24 hours after, product shows good peel value (5N) and does not have adhesive residue.Expansion value lower (2N).

Example 3: silicone binder course

Unprocessed urine cover is obtained by Dow CorningC6-540 silicone elastomer.Aluminium axle top scribbling the PTFE coating applies acryloid cement, and it is from the Gelva2853 of UCB-Solutia, and this PTFE coating has the release characteristics for PSA and silicone.Adhesive is dry and vulcanized 2 minutes in the heating furnace of 200 ℃ (effective temperature is 80 ℃).Apply Dow Corning silicone C6-540 with 70% heptane dilution at its top, and (100 ℃ of effective temperatures) presulfurization 2 minutes under 200 ℃.Apply unprocessed urine cover at its top.Heated mandrel is 150 ℃ to effective temperature in 8 minutes then, to guarantee the sulfuration of silicone binder course.At 40 ℃ after following 24 hours, product demonstrates good peel value (5N) and does not have adhesive residue.Expansion value lower (2N).

Example 4: electron beam irradiation

Undressed urine cover carries out preliminary treatment through the electron beam irradiation of a large amount of 2 * 35Gy.Do not use corona pre-treatment.Urinating after cover is placed on the axle that scribbles adhesive, be the Gelva2853 of UCB-Solutia in this case, apply special interpolation sulfuration through roller and discharge the silicone thin layer.Silicone vulcanized in infrared furnace 90 seconds, and the temp of heating element of said infrared furnace is 450 ℃, and the effective temperature that provides is 140 ℃.After being cooled under 50 ℃, the urine cover is rolled from axle, and adhesive is transferred to the inboard of urine cover by axle thus.

At 60 ℃ through after 72 hours; Adhesive is connected on the inboard of urine cover safely; This can test through " pressing test ", and this test is through making adhesive surface contact, with hand both sides peeled off each other immediately then with adhesive surface with the folded urine cover of record book in accordion form.Passing through in the not pretreated reference test of electron beam, adhesive is not peeled off from adhesive, on a side of silicone urine-collecting cover, is almost completely losing efficacy on adhesive-silicone interface but demonstrate.The bigger possibility of adhesive residue on human body skin after this will mean leakage and remove product in using usually." pressing test " carried out with the cover of the urine in example 1,2 and 3, demonstrates adhesive and is fastenedly connected, and this means does not have adhesive to peel off from silicone.In other words, after pressing together, be applied to the adhesive specific viscosity mixture of silicone on the part of corona treatment and be bonded in from more firm on one's body.Should be pointed out that several kinds of different commercial available silicone urine-collecting covers of being processed by dipping process can not pass through this test, but on adhesive-silicone interface, demonstrate partial failure at least.

Example 5: acrylic acid belt

The corona treatment sample with example 1 in identical mode process, and corona treatment partly is cut off.5 kinds of different commercial available acrylates belt and corona treated side are stacked together.The trade name of belt is: " Tesa Window ", " Tesa Multisurface ", " Tesa Transparent Universal ", " Tesa3191 ", " Tesa4049 " and " ImpegaInvisible Tape ".Tested 23 ℃ after following 0.5 hour with 40 ℃ of peel value after following 0.5 hour.Recorded 180 ° of peel value of 5 to 11N, and untreated side has not perhaps been recorded the peel value that is lower than 0.5N through the sample of corona treatment.Lost efficacy on the interface at adhesive-backing at belt under several kinds of situation.This example shows that many different acrylates adhesives can be connected on the silicone material of oxidation processes.Also demonstrate and to use the adhesive that changes by bilateral medical acrylic acid belt through method described herein in the pretreated urine cover.

Claims

1. the silicone external urinary catheter to sulfuration applies the method for adhering skin material, and it comprises:

(a) apply oxidizing process to silicone;

(b) silicone surface to oxidation applies surgical appliance adhesive,

Wherein, surgical appliance adhesive is removed the peel value that required power is surgical appliance adhesive from skin, the peel value of said surgical appliance adhesive less than to the adhesion of silicone to avoid that surgical appliance adhesive is remained on the skin.

2. the method for claim 1 is characterized in that, oxidizing process is carried out through the process of from the group that comprises oxidizing thermal treatment, ultraviolet light, electron beam, gamma radiation and chemical oxidation treatment, selecting.

3. method as claimed in claim 2 is characterized in that, oxidizing thermal treatment is carried out through the processing procedure of from the group that comprises corona treatment, plasma treatment and flame treatment, selecting.

4. the method for claim 1 is characterized in that, jointing material is the polarity jointing material.

5. method as claimed in claim 4 is characterized in that, said polarity jointing material is based on acrylic resin, polyethers, polyvinylether, polyurethane or polyvinylpyrrolidone.

6. the method for claim 1 is characterized in that, jointing material is an acrylic pressure-sensitive adhesive.

7. the method for claim 1 is characterized in that, the silicone structure complete cure.

8. the method for claim 1 is characterized in that, the silicone structure partial vulcanization.

9. method as claimed in claim 2 is characterized in that, oxidizing thermal treatment optionally is applied on the selection part of product.

10. method as claimed in claim 9 is characterized in that oxidizing thermal treatment optionally is applied to the inboard of silicone external urinary catheter.

11. method as claimed in claim 9 is characterized in that, oxidizing thermal treatment is a corona treatment.

12. the external urinary catheter by manufacture of silicones, it comprises,

The oxidation silicone at least in around section, and

Non-oxide silicone outer around section,

Wherein, At least cover interior outward around section around section; External urinary catheter comprises and is positioned at oxidation around the surgical appliance adhesive on the section; Surgical appliance adhesive is removed the peel value that required power is surgical appliance adhesive from skin, the peel value of said surgical appliance adhesive less than to the adhesion of silicone to avoid that surgical appliance adhesive is remained on the skin.

13. silicone urine-collecting cover; It comprises the part of urine cover first side is carried out being fixed on after selective oxidation is handled the surgical appliance adhesive on this part of urine cover first side; Surgical appliance adhesive is removed the peel value that required power is surgical appliance adhesive from skin, the peel value of said surgical appliance adhesive less than to the adhesion of silicone to avoid that surgical appliance adhesive is remained on the skin.

14. silicone urine-collecting cover as claimed in claim 13 is characterized in that, oxidizing process is through being undertaken by the process of selecting in the group that comprises oxidizing thermal treatment, ultraviolet ray, electron beam, gamma radiation and chemical oxidation treatment.

15. silicone urine-collecting cover as claimed in claim 14 is characterized in that, oxidizing thermal treatment is through being undertaken by the processing of selecting in the group that comprises corona treatment, plasma treatment and flame treatment.

16. silicone urine-collecting cover as claimed in claim 13 is characterized in that, jointing material is the polarity jointing material.

17. silicone urine-collecting cover as claimed in claim 16 is characterized in that, said polarity adhesive group is in acrylic resin, polyethers, polyvinylether, polyurethane or polyvinylpyrrolidone.

18. silicone urine-collecting cover as claimed in claim 13 is characterized in that, jointing material is an acrylic pressure-sensitive adhesive.