Item that adheres to the skin

Abstract

Items that adhere to the skin for medical or paramedical use and methods of making and using the same are described.

Claims

1. An item that adheres to the skin, the item comprising: a support S having a top face S1 and a bottom face S2, optionally at least one tie primer C1 applied on at least one part or on all of the top face S1 of the support S, at least one layer D1 applied continuously or discontinuously on the top face S1 of the support S or on the tie primer C1 when it is present, and which comprises a silicone gel E that adheres to the skin, the silicone gel E having the following properties: a) a penetrability of from 80 mm/10 to 300 mm/10, measured according to the standard NF ISO 2137 with a penetrometer having a rod and a cone and the sum of the weights of which is equal to 62.5 g, and b) a tack of from 600 gf/cm.sup.2 to 900 gf/cm.sup.2, for a layer of 200 g/m.sup.2 coated onto a PET support having a thickness of 36 μm and measured according to the standard ASTM D2979, c) an adhesive power of from 1.05 N/cm to 1.25 N/cm, for a layer of 200 g/m.sup.2 coated onto a PET support having a thickness of 36 μm and measured according to the FINAT no. 1 test method by bringing into contact with a strip of Bristol paper into contact with a peel angle of 180°, and d) a static shear strength at 23° C. greater than 3 hours measured according to the FINAT no. 8 test method for a layer of 200 g/m.sup.2 coated onto a PET support having a thickness of 36 μm; and optionally at least one protective layer F comprising a peel-off protective material and applied on the layer D1, the silicone gel E being obtained by crosslinking of a silicone composition X comprising: 1) at least one organopolysiloxane A comprising, per molecule, at least two C.sub.2-C.sub.6 alkenyl radicals each bonded to a silicon atom and consisting of: (i) at least two units of formula (A1):
(Y).sub.a(Z).sub.bSiO.sub.(4−(a+b)/2  (A1) in which: Y represents a C.sub.2 to C.sub.6 alkenyl group, Z represents a monovalent hydrocarbon-based group chosen from alkyl groups having from 1 to 8 carbon atoms inclusive, cycloalkyl groups, and aryl groups; a and b represent integers, a being 1, 2 or 3, b being 0, 1 or 2 and (a+b) being 2 or 3; (ii) and optionally at least one unit of formula (A2):
(Z).sub.cSiO.sub.(4−c)/2  (A2) in which: Z has the same meaning as above, and c represents an integer which is 2 or 3, 2) at least one organopolysiloxane B comprising, per molecule, at least two hydrogen atoms each bonded to a silicon atom, 3) at least one hydrosilylation catalyst C, 4) at least one hydrosilylation reaction inhibitor D, 5) optionally at least one additive K, and 6) from 1.5% to 3.5% by weight, relative to the total weight of the silicone composition X, of at least one silicone resin Z having alkenyl groups bonded to silicon atoms and comprising: a) at least one siloxyl unit of formula (I): $\begin{array}{cc}{\mathrm{YR}}_a{\mathrm{SiO}}_{\frac{\left(3-a\right)}{2}}& \left(I\right)\end{array}$ in which: Y represents a C.sub.2 to C.sub.6 alkenyl group, R is a monovalent hydrocarbon-based group chosen from alkyl groups having from 1 to 8 carbon atoms inclusive, cycloalkyl groups, and aryl groups, and a=0, 1 or 2, b) at least one siloxy unit of formula (II): $\begin{array}{cc}{R}_b{\mathrm{SiO}}_{\frac{\left(4-b\right)}{2}}& \left(\mathrm{II}\right)\end{array}$ in which R has the same definition as above and b=1, 2 or 3; and c) at least one siloxy unit Q of formula (III): $\begin{array}{cc}{\mathrm{SiO}}_{\frac{4}{2}}& \left(\mathrm{III}\right)\end{array}$ with the following conditions: a) the value of the ratio RH.sub.alk=n.sub.H/t.sub.Alk is included in the following range: 0.10≤RH.sub.alk≤0.80, with n.sub.H=number of moles of hydrogen atom directly bonded to a silicon atom of the organopolysiloxane B and t.sub.Alk=number of moles of alkenyl directly bonded to a silicon atom of the organopolysiloxane A and of the silicone resin Z, and b) the dynamic viscosity of the silicone composition X is from 200 mPa.Math.s to 100 000 mPa.Math.s at 25° C.

2. The item as claimed in claim 1, comprising the at least one tie primer C1.

3. The item as claimed in claim 1, wherein the silicone resin Z is selected from the group consisting of: a silicone resin Z.sup.1 of formula MD.sup.ViQ in which: M is a siloxy unit of formula R.sub.3SiO.sub.1/2 in which R is a C.sub.1 to C.sub.8 alkyl or an aryl group, D.sup.Vi is a siloxy unit of formula RR.sup.1SiO.sub.2/2 with R being a C.sub.1 to C.sub.8 alkyl or an aryl group and R.sup.1 being a vinyl group, and Q is a siloxy unit of formula SiO.sub.4/2; a silicone resin Z.sup.2 of formula MM.sup.ViQ in which: M is a siloxy unit of formula R.sub.3SiO.sub.1/2 in which R is a C.sub.1 to C.sub.8 alkyl or an aryl group, M.sup.Vi is a siloxy unit of formula R.sub.2(Vi)SiO.sub.1/2 with Vi being a vinyl group and R being a C.sub.1 to C.sub.8 alkyl group or an aryl group, and Q is a siloxy unit of formula SiO.sub.4/2, and mixtures of the silicone resins Z.sup.1 and Z.sup.2.

4. The item as claimed in claim 1, wherein the silicone composition X comprises at least two different organopolysiloxanes B which are: a) a chain extender Bert comprising: end monovalent siloxy units, which are identical or different, of formula (M):
(H).sub.p(R.sup.1).sub.qSiO.sub.1/2  (M) in which the symbol R.sup.1 corresponds to a C.sub.1 to C.sub.8 alkyl group; the symbol H represents a hydrogen atom and with p=0 or 1, q=2 or 3 and (p+q)=3; divalent siloxy units, which are identical or different, of formula (D):
(H).sub.n(R.sup.2).sub.mSiO.sub.2/2  (D) in which the radical R.sup.2 corresponds to a C.sub.1 to C.sub.8 alkyl group or an aryl group, the symbol H represents a hydrogen atom and with n=0 or 1, m=1 or 2 and (n+m)=2, and with the condition according to which the chain extender B.sup.ext comprises, per molecule, two hydrogen atoms each bonded to a different silicon atom, that is to say two Si—H functions per molecule; b) a crosslinking agent B.sup.ret comprising: at least three siloxy units of formula (B.1):
(H)(L).sub.eSiO.sub.(3−e)/2  (B.1) in which the symbol H represents a hydrogen atom, the symbol L represents an alkyl having from 1 to 8 carbon atoms inclusive or an aryl, and the symbol e is equal to 0, 1 or 2; and optionally other siloxy units of formula (B-2):
(L)gSiO(4−g)/2 in which the symbol L represents an alkyl having from 1 to 8 carbon atoms inclusive and the symbol g is equal to 0, 1, 2 or 3.

5. The item as claimed in claim 1, wherein the at least one organopolysiloxane A comprises at least two organopolysiloxanes A1 and A2 comprising, per molecule, at least two C.sub.2 to C.sub.6 alkenyl radicals each bonded to a silicon atom, wherein: a) the organopolysiloxane A1 has a dynamic viscosity at 25° C. of from 100 mPa.Math.s to 120 000 mPa.Math.s, and b) the organopolysiloxane A2 is a gum having a consistency at 25° C. of from 500 mm/10 to 1000 mm/10.

6. The item as claimed in claim 1, wherein the silicone composition X comprises at least three organopolysiloxanes A comprising, per molecule, at least two C.sub.2 to C.sub.6 alkenyl radicals each bonded to a silicon atom: a) the first having a dynamic viscosity of from 100 mPa.Math.s to 5000 mPa.Math.s, b) the second having a dynamic viscosity of from 5000 mPa.Math.s to 15 000 mPa.Math.s, and c) the third having a dynamic viscosity of from 15 000 mPa.Math.s to 100 000 mPa.Math.s.

7. The item as claimed in claim 1, wherein the support S is composed of a nonwoven material, of a knitted or woven textile material, or of a plastic film.

8. The item as claimed in claim 1, wherein the support S is a perforated flexible polyurethane film or a continuous flexible polyurethane film.

9. The item as claimed in claim 1, comprising one or more layers N comprising an absorbent substance O, optionally separated by one or more intermediate layers P, placed on the support S on the side of the bottom face S2 of the support S.

10. The item as claimed in claim 1, wherein the support S is a flexible polyurethane film and comprises, on at least one part of the bottom face S2, a pressure-sensitive adhesive.

11. The item as claimed in claim 1, wherein it is a dressing, a part of a dressing, or a part of a medical device for holding a sensor, probe, catheter, needle or ostomy bag in contact with the skin.

12. The item as claimed in claim 1, wherein the penetrability of the silicone gel E is from 80 mm/10 to 200 mm/10.

13. The item as claimed in claim 1, wherein the tack of the silicone gel E is from 700 gf/cm.sup.2 to 850 gf/cm.sup.2.

14. The item as claimed in claim 1, wherein the adhesive power of the silicone gel E is from 1.10 N/cm to 1.20 N/cm.

15. The item as claimed in claim 1, wherein the Y in formula (A1) is a vinyl group.

16. The item as claimed in claim 1, wherein when the Z is an alkyl group having 1 to 8 carbons, Z is a methyl, ethyl, propyl or 3,3,3-trifluoropropyl group.

17. The item as claimed in claim 1, wherein when the Z is a cycloalkyl group, Z is a cyclohexyl, cycloheptyl or cyclooctyl group.

18. The item as claimed in claim 1, wherein when the Z is an aryl group, Z is a xylyl, tolyl or phenyl group.

19. The item as claimed in claim 1, wherein the at least one polyorganosiloxane B comprises at least three hydrogen atoms each bonded to a silicon atom.

20. The item as claimed in claim 1, wherein the silicone composition X comprises 1.75% to 3.0% by weight of at least one silicone resin Z.

21. The item as claimed in claim 1, wherein the Y in formula (I) is a vinyl group.

22. The item as claimed in claim 1, wherein when the R is an alkyl group having 1 to 8 carbon atoms, R is a methyl, ethyl, propyl or 3,3,3-trifluoropropyl group.

23. The item as claimed in claim 1, wherein when the R is a cycloalkyl group, R is a cyclohexyl, cycloheptyl or cyclooctyl group.

24. The item as claimed in claim 1, wherein when the R is an aryl group, R is a xylyl, tolyl or phenyl group.

25. The item as claimed in claim 1, wherein in formula I a=1 or 2.

26. The item as claimed in claim 1, wherein the value of the ratio RH.sub.alk=n.sub.H/t.sub.Alk is included in the range 0.20≤RH.sub.alk≤0.80.

27. The item as claimed in claim 1, wherein the value of the ratio RH.sub.alk=n.sub.H/t.sub.Alk is included in the range range 0.20≤RH.sub.alk≤0.75.

28. The item as claimed in claim 1, wherein the dynamic viscosity of the silicone composition X is from 200 mPa.Math.s to 80,000 mPa.Math.s at 25° C.

29. The item as claimed in claim 2, wherein the penetrability of the silicone gel E is from 80 mm/10 and 200 mm/10.

30. The item as claimed in claim 2, wherein the tack of the silicone gel E is from 700 gf/cm.sup.2 to 850 gf/cm.sup.2.

31. The item as claimed in claim 2, wherein the adhesive power of the silicone gel E is from 1.10 N/cm to 1.20 N/cm.

32. The item as claimed in claim 2, wherein the Y in formula (A1) is a vinyl group.

33. The item as claimed in claim 2, wherein when the Z is an alkyl group having 1 to 8 carbons, Z is a methyl, ethyl, propyl or 3,3,3-trifluoropropyl group.

34. The item as claimed in claim 2, wherein when the Z is a cycloalkyl group, Z is a cyclohexyl, cycloheptyl or cyclooctyl group.

35. The item as claimed in claim 2, wherein when the Z is an aryl group, Z is a xylyl, tolyl or phenyl group.

36. The item as claimed in claim 2, wherein the at least one polyorganosiloxane B comprises at least three hydrogen atoms each bonded to a silicon atom.

37. The item as claimed in claim 2, wherein the silicone composition X comprises 1.75% to 3.0% by weight of at least one silicone resin Z.

38. The item as claimed in claim 2, wherein the Y in formula (I) is a vinyl group.

39. The item as claimed in claim 2, wherein when the R is an alkyl group having 1 to 8 carbon atoms, R is a methyl, ethyl, propyl or 3,3,3-trifluoropropyl group.

40. The item as claimed in claim 2, wherein when the R is a cycloalkyl group, R is a cyclohexyl, cycloheptyl or cyclooctyl group.

41. The item as claimed in claim 2, wherein when the R is an aryl group, R is a xylyl, tolyl or phenyl group.

42. The item as claimed in claim 2, wherein in formula (I), a=1 or 2.

43. The item as claimed in claim 2, wherein the value of the ratio RH.sub.alk=n.sub.H/t.sub.Alk is included in the range 0.20≤RH.sub.alk≤0.80.

44. The item as claimed in claim 2, wherein the value of the ratio RH.sub.alk=n.sub.H/t.sub.Alk is included in the range 0.20≤RH.sub.alk≤0.75.

45. The item as claimed in claim 2, wherein the dynamic viscosity of the silicone composition X is from 200 mPa.Math.s to 80,000 mPa.Math.s at 25° C.

46. The item as claimed in claim 3, wherein the R in the M of the resin Z.sup.1 is a xylyl, tolyl or phenyl group.

47. The item as claimed in claim 3, wherein the R in the M of the resin Z.sup.2 is a xylyl, tolyl or phenyl group.

48. The item as claimed in claim 3, wherein the R in the M.sup.Vi of the resin Z.sup.2 is a xylyl, tolyl or phenyl group.

49. The item as claimed in claim 4, wherein the L in formula (B.1) is a xylyl, tolyl or phenyl group.

Description

EXAMPLES

(1) 1) Measurement of the Tack:

(2) The test is carried out according to the standard ASTM D2979 with a PROBE TACK device (PT-1000). A cylindrical punch with a flat face is brought into contact with the gel of the composite to be tested (surface area of contact with the gel=0.2 cm.sup.2). The composite consists of a PET support (thickness of 36 μm) coated with 200 g/m.sup.2 of the precursor silicone composition for the gel. The punch is then kept in contact with the gel for a contact time of 1 second at a constant pressure of 100 gf/cm.sup.2. Next, the punch is detached from the gel at a constant speed of 10 mm/s, and the force required to separate the gel from the rod is measured and expressed in gf/cm.sup.2.

(3) 2) The adhesive power at 180° or peel test at 180°

(4) The composite consists of a PET support (thickness of 36 μm) coated with 200 g/m.sup.2 of the precursor silicone composition for the gel. The adhesive power at 180° is evaluated by the method described in the document FINAT Test Method n° 1 (FINAT Technical Handbook 6th Edition, 2001). Thus, the silicone gel of the composite to be tested (dimensions=15 cm in length and 4 cm in width) is brought into contact with a sheet of Bristol paper (brand-name Exacompta®). The composite is then detached with an angle of 180° with a constant speed of 300 mm/min and with the aid of a 10 N force cell. The force is measured and related to the width of the item and expressed in N/cm.

(5) 3) Static Shear Strength

(6) The composite consists of a PET support (thickness of 36 μm) coated with 200 g/m.sup.2 of the precursor silicone composition for the gel.

(7) The static shear strength is evaluated by means of the method described in the document “FINAT Test Method no. 8” (FINAT Technical Handbook 6th Edition, 2001).

(8) The composite (dimensions: 4.5 cm×2.5 cm) is adhesively bonded to a metal (stainless steel) plate and is subjected to a weight of 1 kg. The time required until the weight drops is measured in hours and corresponds to the shear.

(9) 4) Calculation of the Ratio r.sub.1

(10) $r_1=\frac{\begin{array}{c}\mathrm{Number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{SiH}\\ \mathrm{function}\mathrm{of}\mathrm{the}\mathrm{extruder}{B}^{\mathrm{ext}}\end{array}}{\begin{array}{c}\mathrm{Total}\mathrm{number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{SiH}\mathrm{function}\\ \left(\mathrm{extruder}{B}^{\mathrm{ext}}+\mathrm{crosslinking}\mathrm{agent}{B}^{\mathrm{ret}}\right)\end{array}}\times 100$
5) Preparation of the Gel Precursor Silicone Compositions According to the Invention

(11) a) Starting Materials Used POS A1=α,ω-(dimethylvinylsiloxy) polydimethylsiloxane oil having a dynamic viscosity at 25° C. equal to 60 000 mPa.Math.s. POS A2=α,ω-(dimethylvinylsiloxy) polydimethylsiloxane oil having a dynamic viscosity at 25° C. equal to 10000 mPa.Math.s. POS A3=α,ω-(dimethylvinylsiloxy) polydimethylsiloxane oil having a dynamic viscosity at 25° C. equal to 3500 mPa.Math.s. Silicone resin Z.sup.1: of formula MD.sup.ViQ in which: M is a siloxy unit of formula: (CH.sub.3).sub.3SiO.sub.1/2 D.sup.Vi is a siloxy unit of formula (CH.sub.3)(vinyl)SiO.sub.2/2 Q is a siloxy unit of formula SiO.sub.4/2 Silicone resin Z.sup.2 of formula MM.sup.ViQ in which: M is a siloxy unit of formula (CH.sub.3).sub.3SiO.sub.1/2 M.sup.Vi is a siloxy unit of formula: (CH.sub.3).sub.2(vinyl)SiO.sub.1/2; and Q is a siloxy unit of formula SiO.sub.4/2, EXT=POS B1.sup.ext: poly(dimethylsiloxy)-α, ω-dimethylhydrosiloxy oil having a viscosity of approximately 8.5 mPa.Math.s and containing on average 5.7% by weight of SiH unit; structure of the type: M.sup.HD.sub.xM.sup.H with x between on average 7 and 15; XL=POS B1.sup.ret: poly(dimethylsiloxy) (methylhydrosiloxy) α, ω-dimethylhydrosiloxy oil having an average viscosity of 70 mPa.Math.s and containing approximately 1.9% by weight of SiH group; structure of the type: M.sup.HD.sub.xD.sub.w.sup.HM.sup.H with x between on average 70 and 80 and w on average between 1 and 3; Cata. (C)=platinum organometallic catalyst used as reaction catalyst. ECH=hydrosilylation reaction inhibitor=1-ethynyl-1-cyclohexanol Stabilizer K=phosphoric acid silyl ester.

(12) b) Preparation of the Composites (=Support Coated with a Silicone Gel)

(13) The silicone compositions tested are in the two-component form. The parts called Part A and Part B are then mixed in a 1:1 weight ratio. The precursor silicone composition for a gel is then applied, at a weight of 200 g/m.sup.2, to a PET support (thickness of 36 μm) using a coating scraper. After the coating, the crosslinking of the composite is carried out for 30 min at 120° C. in a ventilated oven so as to obtain a support coated with a gel. For composite n° 1, a gel is used which is obtained from the precursor silicone composition for the gel and sold under the name Gel silicone Silbione® HC2 2022 by the company Bluestar Silicones. For composite n° 2, a gel is used which is obtained from the following silicone composition (mixture of parts A and B, weight ratio 1:1)

(14) TABLE-US-00001 TABLE 1 Composition of the gel for composite n° 2 PART A PART B Constituents % by weight Constituents % by weight POS A1 2.989 POS A1 26.65 POS A2 97.000 POS A2 55.90 Cata. (C) 0.066 ECH 0.012 Silicone resin Z.sup.1 2.50 POS A3 7.50 Stabilizer K 0.04 XL 5.70 EXT 1.74 Formulation n° 2: RH.sub.alk=0.62, weight of silicone resin Z.sup.1=1.25% by weight relative to the total weight of the composition and r1=45%, viscosity after mixing of parts A and B=12 000 mPa.Math.s For composite n° 3, a gel is used which is obtained from the following silicone composition (mixture of parts A and B, weight ratio 1:1)

(15) TABLE-US-00002 TABLE 2 Composition of the gel for composite n° 3 PART A PART B Constituents % by weight Constituents % by weight POS A1 2.989 POS A1 21.96 POS A2 97.000 POS A2 49.49 Cata. (C) 0.066 ECH 0.012 Silicone resin Z.sup.1 5.00 POS A3 15.00 Stabilizer K 0.04 XL 6.60 EXT 2.01 Formulation n° 3: RH.sub.alk=0.62, weight of silicone resin Z.sup.1=2.50% by weight relative to the total weight of the composition and r1=45%, viscosity after mixing of parts A and B=10 000 mPa.Math.s For composite n° 4, a gel is used which is obtained from the following silicone composition (mixture of parts A and B, weight ratio 1:1)

(16) TABLE-US-00003 TABLE 3 Composition of the gel for composite n° 4 PART A PART B Constituents % by weight Constituents % by weight POS A1 2.989 POS A1 25.29 POS A2 97.000 POS A2 56.08 Cata. (C) 0.011 ECH 0.012 Silicone resin Z.sup.2 4.00 POS A3 2.00 POS A1 4.00 Stabilizer K 0.04 XL 6.60 EXT 2.00 Formulation n° 4: RH.sub.alk=0.62, weight of silicone resin Z.sup.2=2% by weight relative to the total weight of the composition and r1=45%, viscosity after mixing of parts A and B=15 000 mPa.Math.s For composite n° 5, a gel is used which is obtained from the following silicone composition (mixture of parts A and B, weight ratio 1:1)

(17) TABLE-US-00004 TABLE 4 Composition of the gel for composite n° 5 PART A PART B Constituents % by weight Constituents % by weight POS A1 2.989 POS A1 21.29 POS A2 97.000 POS A2 47.77 Cata. (C) 0.011 ECH 0.012 Silicone resin Z.sup.2 8.00 POS A3 4.00 POS A1 8.00 Stabilizer K 0.04 XL 8.38 EXT 2.55 Formulation n° 5: RH.sub.alk=0.62, weight of silicone resin Z.sup.2=4% by weight relative to the total weight of the composition and r1=45%, viscosity after mixing of parts A and B=15 000 mPa.Math.s

(18) TABLE-US-00005 TABLE 5 Properties of the composites tested Amount in Composites Silicone the silicone (supports coated resin composition Penetration Peel 200 g/m.sup.2 Tack Shear with silicone gel) tested (%) (mm/10) (N/cm) (gf/cm.sup.2) (hours) no1 0 155 1.03 600 <1 Comparative no2 silicone 1.25 154 1.19 758 3 Comparative resin Z.sup.1 no3 2.50 132 1.16 832 11 Invention no4 silicone 2.00 118 1.14 780 16 Invention resin Z.sup.2 no5 4.00 Not 0.3 292 13.7 Comparative measured

(19) The introduction of the resin Z.sup.1 at 2.50% by weight, relative to the total weight of the composition, or of the resin Z.sup.2 at 2% by weight, relative to the total weight of the composition, makes it possible to achieve optimal performances (all the properties are improved compared with the comparative composite n° 1 and in particular the shear strength) while at the same time retaining the optimal tack properties.