Medical silicone pressure-sensitive adhesive composition

Abstract

The present invention relates to a medical silicone pressure-sensitive adhesive composition comprising: an organopolysiloxane A, an organopolysiloxane resin B, an organopolysiloxane crosslinker XL, an organopolysiloxane extender CE, a hydrosilylation catalyst D, a solvent E, and a hydrosilylation inhibitor F; wherein the organopolysiloxanes A, CE, and XL have a molar ratio RHAlk=tH / tAlk of 3.5 to 8.0, nH XL / nH CE is selected to be 0.13 to 11, where: tH = the number of moles of hydrogen atoms directly bonded to silicon atoms of organopolysiloxanes XL and CE, tAlk = the number of moles of alkenyl directly bonded to silicon atoms of organopolysiloxane A, nH XL = number of moles of hydrogen atoms directly bonded to silicon atoms in organopolysiloxane XL, nH CE = number of moles of hydrogen atoms directly bonded to silicon atoms of the organopolysiloxane CE. The present invention also relates to a method for coating a substrate with this medical silicone pressure-sensitive adhesive composition, a coated substrate obtained according to this method, and a skin-adhesive article using this medical silicone pressure-sensitive adhesive composition.

Description

Technical Field

[0001] The field of the present invention is the field of medical pressure-sensitive adhesives (PSA). Specifically, the present invention relates to a medical silicone pressure-sensitive adhesive composition, a method for coating a substrate using this medical silicone pressure-sensitive adhesive composition, a coated substrate obtained according to this method, and a skin patch article using this medical silicone pressure-sensitive adhesive composition.

Background Art

[0002] PSA is an abbreviation of the term "pressure-sensitive adhesive" and is well-known in the art and widely used in various applications, especially medical applications. Currently, in the medical market, most of the products that come into contact with the skin, such as tapes, patches, and bandages, are manufactured with acrylic PSA. However, acrylic PSA has drawbacks such as poor resistance to sweat (water), poor biocompatibility, and a high sensitization rate to human skin, especially infants and children.

[0003] Silicone-based PSA is also widely used in medical applications where it is applied to or in contact with the skin. Silicone-based PSA can adhere to the surface simply by contact or by applying a light pressure. It has significant advantages compared to acrylic PSA. Silicone-based PSA exhibits advantageous properties for medical applications due to its breathability, water resistance, low irritation, and biocompatibility. For example, due to its biocompatibility and permeability, silicone-based PSA enables the diffusion of oxygen, carbon dioxide, and water vapor, making it suitable for the increasing requirements of new medical applications, and thus optimal for medical applications that require enhanced aeration.

[0004] International Publication No. WO 2017 / 158249 describes a silicone gel that can be used as a skin adhesive. The silicone gel has good adhesiveness on a polyester or polyurethane substrate and has better adhesiveness to the skin than gels of the prior art. Due to its inherent properties, the silicone gel lacks adhesiveness to wet skin, so it can avoid secondary damage to wounds during dressing use and is beneficial for wound care applications. However, in the case of medical materials attached to the skin without causing trauma, the adhesiveness of the gel often decreases due to a wet environment or sweating, and it often peels off.

[0005] Korean Patent No. 10-1731612 describes a medical silicone pressure-sensitive adhesive composition based on a vinyl silicone resin. Compared with conventional acrylic pressure-sensitive adhesives, it is harmless to human skin, has excellent adhesiveness such as initial adhesiveness and re-adhesiveness, and is also excellent in absorbency and wound healing effect. However, this document has not studied medical silicone pressure-sensitive adhesives based on hydroxy silicone resins, nor has it considered the influence of high molecular weight terminal vinyl polysiloxane. Furthermore, the influence of factors such as XL viscosity, tH / tAlk ratio, nH XL / nH CE ratio on the coating performance of medical silicone pressure-sensitive adhesives has not been systematically studied and clearly defined. The residual property of the pressure-sensitive adhesive on the skin after wearing was not evaluated.

[0006] WO 2020 / 099999 describes a medical silicone pressure-sensitive adhesive that enhances adhesion while minimizing skin damage and pain when removing the adhesive. In this document, a condensation product is formed by the reaction of a polyorganosiloxane containing terminal hydroxyl groups with a silicate resin, and then a non-reactive polyorganosiloxane is mixed. In the subsequent tape manufacturing process, an electron beam is used to promote the cross-linking of the non-reactive polyorganosiloxane, thereby forming a layer of pressure-sensitive adhesive on the substrate. In this document, the manufacturing process of the PSA is complex, and the control of the condensation reaction conditions has a great impact on the product quality. An electron beam is required in the subsequent curing process, and the equipment is relatively expensive. Furthermore, the properties of the condensation-type PSA are determined by the prior condensation reaction, and its subsequent applications are limited.

Summary of the Invention

Problems to be Solved by the Invention

[0007] Therefore, there has always been a demand for obtaining a silicone-based pressure-sensitive adhesive composition having excellent overall properties suitable for medical applications.

[0008] The present invention solves the problems of the prior art.

[0009] Specifically, in addition to maintaining the properties of the silicone-based pressure-sensitive adhesive such as its original air permeability, water resistance, low irritation, and biocompatibility, the present invention has an adhesive strength comparable to that of acrylic PSA. Therefore, it may gradually replace acrylic PSA in the medical field, and some new applications where acrylic PSA is not suitable have also been found. The object of the present invention is to provide a medical silicone pressure-sensitive adhesive composition.

[0010] The silicone-based pressure-sensitive adhesive composition of the present invention provides excellent overall properties (such as excellent overall properties such as ease of tearing, invisible residues on the skin, good fixing property to the substrate, good peel adhesion, good tackiness, appropriate peel force, and acceptable re-sticking properties) suitable for medical applications after cross-linking.

[0011] The silicone-based pressure-sensitive adhesive (PSA) composition of the present invention can obtain a silicone-based pressure-sensitive adhesive (PSA) with good fixing force on a substrate (such as substrates like paper, PU (polyurethane), TPU (thermoplastic polyurethane), non-woven fabric, elastic fabric, etc.) after cross-linking, and while avoiding the discomfort caused when peeling such PSA from the skin, it realizes good adhesiveness (or "tack") on the skin.

Means for Solving the Problems

[0012] Therefore, the present invention relates to a medical silicone pressure-sensitive adhesive composition comprising the following: · At least one organopolysiloxane A containing at least two C2-C6 alkenyl radicals each bonded to a silicon atom per molecule, · At least one organopolysiloxane resin B containing a hydroxyl group bonded to a silicon atom, · At least one organopolysiloxane cross-linking agent XL having at least three hydrogen atoms bonded to a silicon atom, · At least one organopolysiloxane extender CE having exactly two terminal hydrogen atoms bonded to a silicon atom, · At least one hydrosilylation catalyst D, · At least one solvent E, · At least one hydrosilylation inhibitor F; Here, Organopolysiloxane A, CE, and XL are selected such that the molar ratio RHAlk = tH / tAlk is 3.5 - 8, and nH XL / nH CE is 0.13 - 11, where: · tH = the number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane XL and CE, · tAlk = the number of moles of alkenyl directly bonded to the silicon atoms of organopolysiloxane A, · nH XL = the number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane XL, · nH CE= The number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane CE.

[0013] The silicone pressure-sensitive adhesive composition for medical use of the present invention is a precursor of silicone pressure-sensitive adhesive G and can be crosslinked by a hydrosilylation reaction.

[0014] Another object of the present invention is to provide a skin patch article comprising a substrate having a silicone pressure-sensitive adhesive formed by crosslinking a silicone pressure-sensitive adhesive composition for medical use containing the following: · At least one organopolysiloxane A containing at least two C2-C6 alkenyl radicals each bonded to a silicon atom per molecule, · At least one organopolysiloxane resin B containing a hydroxyl group bonded to a silicon atom, · At least one organopolysiloxane crosslinking agent XL having at least three hydrogen atoms bonded to a silicon atom, · At least one organopolysiloxane extender CE having exactly two terminal hydrogen atoms bonded to a silicon atom, · At least one hydrosilylation catalyst D, · At least one solvent E, · At least one hydrosilylation inhibitor F; Here, Organopolysiloxanes A, CE, and XL are selected such that the molar ratio RHAlk = tH / tAlk is 3.5 - 8 and nH XL / nH CE is 0.13 - 11, where: · tH = The number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane XL and CE, · tAlk = The number of moles of alkenyl directly bonded to the silicon atoms of organopolysiloxane A, · nH XL = The number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane XL, · nH CE= The number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane CE.

[0015] Another object of the present invention is to provide a method for coating a substrate using the silicone pressure-sensitive adhesive composition of the present invention.

[0016] A further object of the present invention is to provide a coated substrate obtained by the method according to the present invention.

[0017] Still another object of the present invention is to provide a substrate coated with a silicone pressure-sensitive adhesive G formed by crosslinking the silicone pressure-sensitive adhesive composition of the present invention.

Advantages of the Invention

[0018] In order to particularly achieve these objects, the inventors of the present invention conducted numerous experiments using a number of research means. According to the findings of the inventors, by selecting organopolysiloxanes A, CE, and XL such that the molar ratio RHAlk = tH / tAlk is 3.5 to 8 and nH XL / nH CE is 0.13 to 11, a medical silicone pressure-sensitive adhesive composition is obtained, which, after crosslinking, provides excellent comprehensive properties suitable for medical applications (for example, excellent comprehensive properties such as ease of tearing, invisible residues on the skin, good fixing property to the substrate, good peel adhesion, good tackiness, appropriate peel force, and acceptable reattachment properties).

[0019] The inventors of the present invention also found that by selecting components CE and XL such that the nH XL / nH CE ratio is within a specific range according to the end use, the medical silicone pressure-sensitive adhesive composition can be particularly applied to various specific substrates (especially substrates made of paper, TPU, non-woven fabric, and elastic fabric), and as a result, good performance in the end use of PSA is obtained.

Modes for Carrying Out the Invention

[0020] Component A: Organopolysiloxane A Component A can be at least two C2-C6 alkenyl-substituted silicone polymers used as the main chain in the composition.

[0021] According to one embodiment, organopolysiloxane A is an organopolysiloxane gum having a viscosity of 200 mm / 10 to 2000 mm / 10, preferably 300 mm / 10 to 1800 mm / 10, more preferably 500 mm / 10 to 1500 mm / 10 at 25°C.

[0022] According to one embodiment, organopolysiloxane A is an organopolysiloxane gum having a weight average molecular weight Mw of 260,000 g / mol to 1,000,000 g / mol, preferably 400,000 g / mol to 1,000,000 g / mol, more preferably 600,000 g / mol to 900,000 g / mol. The weight average molecular weight Mw is measured by gel permeation chromatography using polystyrene as a standard.

[0023] According to one embodiment, organopolysiloxane A is an organopolysiloxane gum showing a viscosity exceeding 600,000 mPa·s at 25°C, preferably exceeding 1,000,000 mPa·s at 25°C.

[0024] According to another embodiment, the medical silicone pressure-sensitive adhesive composition according to the present invention contains at least two organopolysiloxanes A, wherein the first organopolysiloxane A' is the gum defined above, and the second organopolysiloxane A'' is an oil having a dynamic viscosity of 10 to 500,000 mPa·s, preferably 100 to 100,000 mPa·s, more preferably 10,000 to 100,000 mPa·s at 25°C. Organopolysiloxane A'' may be linear or branched and may have an alkenyl content of 0.05 wt% to 0.5 wt% based on the total weight of component A''.

[0025] All viscosities contemplated herein correspond to the magnitude of the "Newtonian" dynamic viscosity at 25 °C, i.e., the magnitude of the dynamic viscosity measured in a manner known per se using a Brookfield viscometer at a shear gradient low enough so that the measured viscosity is independent of the velocity gradient.

[0026] The consistency or penetration of the gum is measured at 25 °C using a penetrometer of the PNR12 type or equivalent model capable of applying a cylindrical head to the sample under standardized conditions. The penetration of the gum is expressed in tenths of a millimeter as the depth to which a calibrated cylinder penetrates the sample in one minute. In this regard, a sample of the gum is introduced into an aluminum container 40 mm in diameter and 60 mm in height. The cylindrical head, made of bronze or brass, is 6.35 mm in diameter and 4.76 mm in height and is supported by a metal rod 51 mm in length and 3 mm in diameter that fits the penetrometer. A 100 g overload is applied to this rod. The total weight of the assembly is 151.8 g, including 4.3 g for the cylindrical part and its support rod. The container containing the gum sample is placed in a thermostat-controlled bath at 25 ± 0.5 °C for at least 30 minutes. The measurement is carried out according to the manufacturer's instructions. Values of the depth (V) in tenths of a millimeter and the time (t) in seconds to reach this depth are displayed on the device. The penetration is equal to 60V / t and is expressed in tenths of a millimeter per minute.

[0027] Preferably, at least one organopolysiloxane A may comprise: (I) at least two siloxyl units of the formula (A1): (Y) a (Z) b SiO (4-(a+b)) / 2 (A1) wherein, · Y represents a monovalent radical containing 2 to 6 carbon atoms and having at least two alkenyl groups, · Z represents a monovalent radical containing 1 to 20 carbon atoms and not containing an alkenyl group, · a and b represent integers, a is 1, 2 or 3, b is 0, 1 or 2, and (a + b) is 1, 2 or 3; (ii) Optionally, it may contain other siloxyl units of formula (A2): (Z) c SiO (4-c) / 2 (A2) wherein, · Z has the same meaning as above, · c represents an integer of 1, 2, or 3.

[0028] According to the present invention, regarding the definition of the organopolysiloxane A in formula (A1), it is advisable that the symbol a is preferably 1 or 2, and even more preferably equal to 1. Further, in formula (A1) and formula (A2), the symbol Z is preferably a monovalent group selected from the group consisting of an alkyl group containing 1 to 8 carbon atoms (which may be substituted with at least one halogen atom), and a C6 - C 10 aryl group. Z can preferably represent a monovalent group selected from the group consisting of methyl, ethyl, propyl, 3,3,3 - trifluoropropyl, xylyl, tolyl and phenyl. Further, in formula (A1), the symbol Y can preferably represent a group selected from the group consisting of vinyl, propenyl, 3 - butenyl and 5 - hexenyl. Preferably, the symbol Y is vinyl and the symbol Z is methyl.

[0029] The organopolysiloxane A may be linear or branched, but is preferably linear. In the case of a linear organopolysiloxane, it can be essentially composed of: · siloxyl units "D" selected from units of formula (Y)2SiO 2 / 2 , (Y)(Z)SiO 2 / 2 and (Z)2SiO 2 / 2 ; and · siloxyl units "M" selected from units of formula (Y)3SiO 1 / 2 , (Y)2(Z)SiO 1 / 2 , (Y)(Z)2SiO 1 / 2 and (Z)3SiO 2 / 2 ; ·In the formula, the symbols Y and Z are as defined above.

[0030] The degree of polymerization of the linear organopolysiloxane A is preferably in the range of 2,000 to 10,000, more preferably in the range of 2,000 to 8,000, and even more preferably in the range of 2,000 to 5,000.

[0031] Examples of the unit "D" include dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy, and methyldecadienylsiloxy groups.

[0032] Examples of the unit "M" include trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy, and dimethylhexenylsiloxy groups.

[0033] When the organopolysiloxane A is particularly linear, it can be a polymer having a weight average molecular weight Mw of preferably 400,000 g / mol to 1,000,000 g / mol, preferably 600,000 g / mol to 900,000 g / mol.

[0034] Examples of useful organopolysiloxane A include the following: · Polydimethylsiloxane containing dimethylvinylsilyl end groups; · Poly(methylphenylsiloxane-co-dimethylsiloxane) containing dimethylvinylsilyl end groups; · Poly(vinylmethylsiloxane-co-dimethylsiloxane) containing dimethylvinylsilyl end groups; · Poly(dimethylsiloxane-co-vinylmethylsiloxane) containing trimethylsilyl end groups.

[0035] An organopolysiloxane A which is a polydimethylsiloxane having a weight average molecular weight Mw of 260,000 g / mol to 1,000,000 g / mol, preferably 600,000 g / mol to 900,000 g / mol and containing dimethylvinylsilyl end groups is particularly advantageous. A particularly advantageous organopolysiloxane A is of the formula M Vi DaM Vi wherein, ·M Vi = a siloxyl unit of the formula: (vinyl)(CH3)2SiO 1 / 2 ; ·D = a siloxyl unit of the formula: (CH3)2SiO 2 / 2 ; ·a is a numerical value of 2000 to 6000, preferably 3000 to 5500.

[0036] Organopolysiloxane A can be used in an amount of 15 to 45% by weight, preferably 20 to 35% by weight, based on the total amount of components A + B + XL + CE.

[0037] According to one embodiment, organopolysiloxane A has an alkenyl content of 0.001% by weight to 0.5% by weight, preferably 0.005% by weight to 0.025% by weight, more preferably 0.008% by weight to 0.018% by weight, based on the total weight of organopolysiloxane A.

[0038] Preferably, organopolysiloxane A is selected from dimethylvinyl end-polydimethylsiloxane, dimethylvinyl end-polydimethylmethylvinylsiloxane, trimethyl end-polydimethylmethylvinylsiloxane, and more preferably can be selected from dimethylvinyl end-polydimethylsiloxane.

[0039] Component B: Organopolysiloxane resin B containing hydroxyl groups bonded to Si atoms To describe polyorganosiloxanes, the nomenclature known in the field of silicones is used, and the following letters are used to describe siloxy units: M, D, T, and Q. The letter M represents a unit of the formula (R 1 )3SiO 1 / 2represents a monofunctional unit, and the silicon atom is bonded to only one oxygen atom in the polymer containing this unit. The letter D represents a difunctional unit (R 1 )2SiO 2 / 2 in which the silicon atom is bonded to two oxygen atoms. The letter T represents a trifunctional unit of the formula (R 1 )SiO 3 / 2 in which the silicon atom is bonded to three oxygen atoms. The letter Q represents a tetrafunctional unit of the formula SiO 4 / 2 in which the silicon atom is bonded to four oxygen atoms. The symbol R 1 has the same definition as the symbol R 2 . The M, D, and T units can be functionalized. Next, the M, D, and T units will be referred to while specifying certain radicals.

[0040] As the organopolysiloxane resin B in which a hydroxyl group is bonded to the Si atom, it can be selected from conventionally known organopolysiloxane resins. Among them, the co-hydrolysis and co-condensation of chlorosilanes selected from the group consisting of (R 2 )3SiCl, (R 2 )2Si(Cl)2, R 2 Si(Cl)3, and Si(Cl)4 can be mentioned. These resins are well-known and are commercially available branched organopolysiloxane oligomers or polymers. In their structure, they show at least two different siloxyl units selected from the formula (R 2 )3SiO 1 / 2 (M unit), (R 2 )2SiO 2 / 2 (D unit), R 2 SiO 3 / 2 (T unit), and SiO 4 / 2 (Q unit), and at least one of these units is a T unit or a Q unit. The R 2 radicals are distributed such that the resin contains about 0.8 to 1.8 R 2 radicals per silicon atom. Furthermore, these resins are not completely condensed and contain OH groups. R 2The radicals are the same or different and are selected from linear or branched C1-C6 alkyl radicals, C2-C4 alkenyl radicals, phenyl or 3,3,3-trifluoropropyl. For example, alkyl R 2 Examples of the radical include methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals, and examples of the alkenyl radical include vinyl or allyl groups. Preferably, R 2 radical is a methyl group or a hydroxyl group.

[0041] According to a particular embodiment, the organopolysiloxane resin B containing a hydroxyl group is selected from the group consisting of: a) M and Q of the following formula (OH) MQ copolymer containing siloxy units (OH) type of hydroxylated silicone resin: ·M = R 3 R 4 R 5 SiO 1 / 2 and ·Q (OH) =(OH)SiO 3 / 2 ; ·Optionally, siloxy unit Q = SiO 4 / 2 is present; b) M, D of the following formula Vi and Q (OH) MD copolymer containing siloxy units Vi Q (OH) type of hydroxylated silicone resin: ·M = R 3 R 4 R 5 SiO 1 / 2 ; ·D Vi =(Vi)(R 3 )SiO 2 / 2 and ·Q (OH) =(OH)SiO 3 / 2 ; ·Optionally, siloxy unit Q = SiO 4 / 2 is present; c) M, M of the following formula Vi and Q (OH)MM, a copolymer containing siloxy units Vi Q (OH) Types of Hydroxysilicone Resin: M=R 3 R 4 R 5 SiO 1 / 2 , M Vi =(Vi)(R 3 )(R 4 )SiO 2 / 2 , and Q (OH) =(OH)SiO 3 / 2 , Optionally, the siloxy unit Q=SiO 4 / 2 exists; d) M, D, and T in the following formula (OH) and MDT, a copolymer containing T siloxy units. (OH) T-type silicone hydroxyl resin: M=R 3 R 4 R 5 SiO 1 / 2 , D=R 3 R 4 SiO 2 / 2 , T (OH) =(OH)R 3 SiO 2 / 2 , T=R 3 SiO 3 / 2 and e) D and T in the following formula (OH) and DT, a copolymer containing T siloxy units. (OH) T-type silicone hydroxyl resin: D=R 3 R 4 SiO 2 / 2 , T (OH) =(OH)R 3 SiO 2 / 2 , T=R 3 SiO 3 / 2 ; In the formula, the symbol Vi represents a vinyl group, and the symbol R 3 , R 4 , and R 5are, independently of each other, selected from the following: · a linear or branched alkyl group having 1 to 8 carbon atoms (optionally substituted with one or more halogen atoms), preferably selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl and n-hexyl groups; · an aryl group or an alkylaryl group having 6 to 14 carbon atoms, preferably selected from the group consisting of phenyl, xylyl and tolyl groups.

[0042] According to a preferred embodiment, the organopolysiloxane resin B includes, for example, an organopolysiloxane resin B selected from at least one of MQ resin, MDQ resin, DT resin and MDT resin, and the OH group can be carried on the Q and / or T units.

[0043] According to another preferred embodiment, the organopolysiloxane resin B is an MQ (OH) , MQQ (OH) or MM Vi Q (OH) type of silicone hydroxide resin, and contains 0.1 to 4% by weight, preferably 0.3 to 2.0% by weight, more preferably 0.5 to 1.5% by weight of hydroxyl groups based on the dry weight of the organopolysiloxane resin B. Preferably, the ratio of M unit to Q unit is 0.5 to 1.2, preferably 0.6 to 0.9. Component B can have a weight average molecular weight Mw of 3000 g / mol to 10000 g / mol, preferably 4000 g / mol to 6000 g / mol.

[0044] In the composition of the present invention, the organopolysiloxane resin B can be used as an adhesion-imparting agent.

[0045] The organopolysiloxane resin B can be used in an amount of 15 to 45% by weight, preferably 25 to 40% by weight, based on the total amount of components A + B + XL + CE.

[0046] Preferably, the weight ratio of component B to component A is 0.8 to 2.5, preferably 1.0 to 2.0.

[0047] Component XL: Organopolysiloxane crosslinking agent XL Component XL, also referred to as a crosslinking agent, is an organopolysiloxane having at least three hydrogen atoms bonded to Si.

[0048] For example, the organohydrogensiloxane crosslinking agent XL according to the present invention may include the following: · At least three siloxyl units of formula (XL-1): (H)(L) e SiO (3-e) / 2 (XL-1) In the formula, the symbol H represents a hydrogen atom, the symbol L represents an alkyl containing 1 to 8 carbon atoms or C6 - C 10 aryl, and the symbol e is equal to 0, 1, or 2; · Optionally, other siloxyl units of formula (XL-2): (L) g SiO (4-g) / 2 (XL-2) In the formula, the symbol L represents an alkyl containing 1 to 8 carbon atoms or C6 - C 10 aryl, and the symbol g is equal to 0, 1, 2, or 3; and · The organopolysiloxane XL has the condition that it contains 0.5 wt% - 15.0 wt% of Si - H functional groups per polymer, preferably 1.0 wt% - 12.5 wt% of Si - H functional groups per polymer, and even more preferably 1.5 wt% - 10.0 wt% of Si - H functional groups per polymer.

[0049] Examples of the organopolysiloxane XL having a crosslinking function and used according to the present invention include M H D x D w H M H M H D x D y H M and MD x D z H M. In these formulas, · M H = formula: (H)(CH3)2SiO 1 / 2Siloxyl units ·D H = Formula: (H)(CH3)SiO 2 / 2 Siloxy units ·D = Formula: (CH3)2SiO 2 / 2 Siloxyl units, ·M = Formula: (CH3)3SiO 1 / 2 , Siloxyl units · However, x is a number from 0 to 500, preferably from 2 to 250, more preferably from 5 to 80, w is a number from 1 to 500, preferably from 1 to 250, or from 1 to 100, even more preferably from 1 to 70, y is a number from 2 to 500, preferably from 3 to 250, or from 2 to 100, even more preferably from 2 to 70, z is a number from 3 to 500, preferably from 3 to 250, or from 3 to 100, more preferably from 3 to 70, and contains 0.5 wt% to 15.0 wt% of Si-H functional groups per polymer, preferably 1.0 wt% to 12.5 wt% of Si-H functional groups per polymer, even more preferably 1.5 wt% to 10.0 wt% of Si-H functional groups per polymer.

[0050] By adjusting the viscosity of Component XL, the medical silicone pressure-sensitive adhesive composition can be specifically applied to various specific substrates, and good performance can be obtained in the final application of the PSA.

[0051] Component XL can have a dynamic viscosity of 40 to 1000 mPa·s at 25°C, preferably 50 to 750 mPa·s at 25°C, more preferably 60 to 500 mPa·s at 25°C. When the viscosity of Component XL is less than 40 mPa·s at 25°C, the bonding strength of the cured PSA is too strong and it cannot be easily torn. It was confirmed that when the bonding strength is strong, the adhesive force to the substrate becomes weak, and when the cured PSA layer is peeled off, a part may remain on the skin.

[0052] Component XL may have an Si-H content of 0.5 wt% to 15 wt%, preferably 1.0 wt% to 12.5 wt%, more preferably 1.5 wt% to 10.0 wt% based on the total weight of Component XL.

[0053] Preferably, the organopolysiloxane crosslinking agent XL can be trimethylsiloxy-terminated polymethylhydrogen siloxane or dimethylhydrogen-terminated polymethylhydrogen siloxane.

[0054] Component CE: Organopolysiloxane extender CE Component CE can be referred to as an extender and is an organopolysiloxane having exactly two terminal hydrogen atoms bonded to Si.

[0055] For example, the organohydrogensiloxane extender CE according to the present invention may include the following: · Two siloxyl terminal units of formula (CE-1) (which may be the same or different): (H) p (R 6 ) q SiO 1 / 2 (CE-1) In the formula, the symbol R 6 corresponds to a C1-C8 alkyl group or a C6-C 10 aryl group, the symbol H represents a hydrogen atom, p = 1, q = 2; · At least one siloxyl unit of formula (CE-2): (H) n (R 7 ) m SiO 2 / 2 (CE-2) In the formula, the radical R 7 corresponds to a C1-C8 alkyl group or a C6-C 10 aryl group, the symbol H represents a hydrogen atom, n = 0, m = 2; and, · The organopolysiloxane CE contains two hydrogen atoms, provided that each hydrogen atom is bonded to a different silicon atom per polymer. Preferably, the organopolysiloxane CE contains two siloxyl units of formula (CE-1) with p = 1 and at least one siloxyl unit of formula (CE-2) with n = 0 per polymer.

[0056] Examples of the organopolysiloxane CE having the function of "chain extender" include polydimethylsiloxane containing dimethylhydrosilyl end groups with a dynamic viscosity of 1 mPa·s at 25°C to 1000 mPa·s at 25°C, preferably 5 mPa·s at 25°C to 500 mPa·s at 25°C, more preferably 5 to 300 mPa·s at 25°C. Particularly advantageous organopolysiloxane CE has the formula M H D x M H wherein, · ML = siloxyl unit of the formula: (H)(CH3)2SiO 1 / 2 · D = siloxyl unit of the formula: (CH3)2SiO 2 / 2 · D = siloxyl unit of the formula: (CH3)2SiO 2 / 2 · x is an integer from 1 to 200, preferably from 1 to 150, more preferably from 3 to 120.

[0057] When the SiH reactive functional group is at the chain end, the organopolysiloxane CE is called a "chain extender" because it is presumed to have the effect of increasing the mesh size of the network during crosslinking.

[0058] Component CE can have a dynamic viscosity of 1 to 1000 mPa·s at 25°C, preferably 5 to 500 mPa·s at 25°C, more preferably 5 to 300 mPa·s at 25°C.

[0059] Component CE can have an Si-H content of 0.2 wt% to 10 wt%, preferably 0.3 wt% to 8.0 wt%, more preferably 0.4 wt% to 6.0 wt% based on the total weight of component CE.

[0060] Preferably, the organopolysiloxane extender CE can be dimethylhydrogen-terminated polydimethylsiloxane.

[0061] The organopolysiloxane crosslinking agent XL and the organopolysiloxane extender CE can be introduced into the composition according to the present invention in any suitable form. For example, the organopolysiloxane crosslinking agent XL and the organopolysiloxane extender CE can be used separately or as a mixture.

[0062] When the organopolysiloxane crosslinking agent XL and the organopolysiloxane extender CE are introduced in the form of a mixture, the mixture is introduced in an amount of 1.0 to 5.0% by weight, preferably 1.0 to 2.0% by weight, based on the total amount of components A + B + XL + CE. The mixture can have a dynamic viscosity of at least 70 mPa·s at 25°C.

[0063] Component D: Hydrosilylation catalyst D Examples of the hydrosilylation catalyst D useful according to the present invention include compounds of metals belonging to the platinum group well-known to those skilled in the art. The metals of the platinum group are metals known as platinumoids in addition to platinum, ruthenium, rhodium, palladium, osmium, and iridium. Compounds of platinum and rhodium are preferably used. In particular, platinum complexes and organic products (described in U.S. Patent Nos. 3,159,601, 3,159,602, 3,220,972, and European Patent Application Publications Nos. 0057459, 0188978, 0190530), complexes of platinum and vinyl organosiloxanes (described in U.S. Patent No. 3,419,593) can be used. Generally preferred catalysts are platinum. By way of example, especially platinum black, chloroplatinic acid, chloroplatinic acid modified with alcohol, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes or acetylene alcohols can be mentioned. Karstedt solutions or complexes as described in U.S. Patent Application Publication No. 3,775,452, chloroplatinic acid hexahydrate, or platinum catalysts containing carbene ligands are preferred.

[0064] Preferably, component D is a solution of a platinum complex in vinyl-terminated polydimethylsiloxane.

[0065] Component E: Solvent E According to one embodiment of the present invention, solvent E is selected from the group consisting of: aliphatic C6-C 16 hydrocarbons, polydimethylsiloxanes containing trimethylsilyl end groups having a viscosity of 0.65 to 5 mPa·s at 25°C, cyclic polydimethylsiloxanes, (3-octyl)heptamethyltrisiloxane, toluene, xylene, C1-C8 alkyl esters, C2-C4 carboxylic acids, and mixtures thereof.

[0066] In particular, solvent E is at least one solvent. Solvent E is at least one medically approved solvent. For example, it is selected from toluene, xylene, heptane, ethyl acetate, and more preferably ethyl acetate for healthcare applications.

[0067] The amount of solvent E is 30% to 80% by weight, preferably 40% to 70% by weight, based on the total weight of the composition.

[0068] Component F: Hydrosilylation inhibitor F A hydrosilylation inhibitor F is used in the present composition.

[0069] Examples of inhibitors of the hydrosilylation reaction used according to the present invention include those selected from α-acetylene alcohols, α,α'-acetylene diesters, enyne conjugated compounds, α-acetylene ketones, acrylonitrile, maleates, fumarates, and mixtures thereof. These compounds that can serve as hydrosilylation inhibitors are well known to those skilled in the art. These can be used alone or as a mixture.

[0070] α-acetylene alcohol type inhibitors can be selected from compounds of the following formula (F1): (R 8 )(R 9 )C(OH)-C≡CH (F1) In the formula, ·R 8 The group represents an alkyl group, a cycloalkyl group, a (cycloalkyl)alkyl group, a C6-C 10 aryl group or a C7-C 18 arylalkyl group, ·R 9 The group represents a hydrogen atom, an alkyl group, a cycloalkyl group, a (cycloalkyl)alkyl group, a C6-C 10 aryl group or a C7-C 18 arylalkyl group, ·Alternatively, R 8 and R 9 together with the carbon atom to which they are attached form a 5-, 6-, 7- or 8-membered aliphatic ring (optionally substituted one or more times).

[0071] According to formula (F1): ·The term "alkyl" is understood to mean a saturated hydrocarbon chain containing 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. The alkyl group can be selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1,1-dimethylpropyl. ·The term "cycloalkyl" is understood, according to the present invention, to mean a saturated monocyclic or polycyclic, preferably monocyclic or bicyclic, hydrocarbon group containing 3 to 20 carbon atoms, preferably 5 to 8 carbon atoms. When the cycloalkyl group is polycyclic, the plurality of cyclic nuclei can be bonded to each other via a covalent bond and / or via a spiro atom, and / or can be condensed with each other. The cycloalkyl group can be selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane and norbornane. ·The term "(cycloalkyl)alkyl" is understood, according to the present invention, to mean a cycloalkyl group as defined above bonded to an alkyl group as defined above. · According to the present invention, the term "aryl" is understood to mean a monocyclic or polycyclic aromatic hydrocarbon group containing 6 to 10 carbon atoms. The aryl group can be selected from the group consisting of phenyl, naphthyl, and anthracenyl. · According to the present invention, the term "arylalkyl" is understood to mean an aryl group as defined above bonded to an alkyl group as defined above.

[0072] According to a preferred embodiment, in formula (F1), R 8 and R 9 together with the carbon atom to which they are attached form an unsubstituted 5-, 6-, 7- or 8-membered aliphatic ring. According to another preferred embodiment, R 8 and R 9 are the same or different and independently of one another represent a monovalent C1-C 12 , preferably a C1-C6 alkyl group.

[0073] The inhibitor containing an α-acetylene alcohol used according to the present invention can be selected from the group consisting of the following compounds: 1-ethynyl-1-cyclopentanol; 1-ethynyl-1-cyclohexanol (also known as ECH); 1-ethynyl-1-cycloheptanol; 1-ethynyl-1-cyclooctanol; 3-methyl-1-butyn-3-ol (also known as MBT); 3-methyl-1-pentyn-3-ol; 3-methyl-1-hexyn-3-ol; 3-methyl-1-heptyn-3-ol; 3-methyl-1-octyn-3-ol; 3-methyl-1-nonyn-3-ol; 3-methyl-1-decyn-3-ol; 3-methyl-1-dodecyn-3-ol; 3-methyl-1-pentadecyn-3-ol; 3-ethyl-1-pentyn-3-ol; 3-ethyl-1-hexyn-3-ol; 3-ethyl-1-heptyn-3-ol; 3,5-dimethyl-1-hexyn-3-ol; 3-isobutyl-5-methyl-1-hexyn-3-ol; 3,4,4-trimethyl-1-pentyn-3-ol; 3-ethyl-5-methyl-1-heptyn-3-ol; 3,6-diethyl-1-nonyn-3-ol; 3,7,11-trimethyl-1-dodecyn-3-ol (also known as TMDDO); 1,1,-diphenyl-2-propyn-1-ol; 3-butyn-2-ol; 1-pentyn-3-ol; 1-hexyn-3-ol; 1-heptyn-3-ol; 5-methyl-1-hexyn-3-ol; 4-ethyl-1-octyn-3-ol and 9-ethynyl-9-fluorenol.

[0074] The α,α'-acetylene diester-based inhibitor can be selected from the compounds of the following formula (F2): [Chemical formula] In the formula, R 10 and R 11 are the same or different and are independent of each other and represent an alkyl group, a cycloalkyl group, a (cycloalkyl)alkyl group, a C6-C 10 aryl group, a C7-C 18 arylalkyl group or a silyl group.

[0075] According to the present invention, the term "silyl" is understood to mean a group of the formula -SiR3, where each R symbol independently represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 8 carbon atoms. The silyl group can be, for example, a trimethylsilyl group.

[0076] According to a specific embodiment, in formula (F2), R 10 and R 11 are the same or different and independently of one another represent a C1 - C 12 , preferably a C1 - C6 alkyl group or a trimethylsilyl group. The inhibitor, which is an α,α'-acetylene diester used according to the present invention, can be selected from the group consisting of the following compounds: dimethyl acetylenedicarboxylate (DMAD), diethyl acetylenedicarboxylate, di(tert-butyl) acetylenedicarboxylate, bis(trimethylsilyl) acetylenedicarboxylate.

[0077] The inhibitor of the en-yne conjugate compound type can be selected from the compounds of the following formula (F3):

Chemical formula

[0078] According to a specific embodiment, R 12 , R 13 and R 14 groups independently of one another represent a hydrogen atom, a C1 - C12 , preferably C1-C6, an alkyl group or C6-C 10 represents an aryl group. The inhibitor, which is an en-yne conjugated compound used according to the present invention, can be selected from the group consisting of the following compounds: 3-methyl-3-penten-1-yne; 3-methyl-3-hexen-1-yne; 2,5-dimethyl-3-hexen-1-yne; 3-ethyl-3-buten-1-yne; and 3-phenyl-3-buten-1-yne. According to another specific embodiment, R 12 , R 13 , and R 14 Among the groups, at least two groups together with the carbon atom(s) to which they are attached form an unsubstituted 5-membered, 6-membered, 7-membered or 8-membered aliphatic ring, and the remaining third group represents a hydrogen atom or a C1-C 12 , preferably an alkyl group of C1-C6. The inhibitor, which is an en-yne conjugated compound used according to the present invention, can be 1-ethynyl-1-cyclohexene.

[0079] The α-acetylene ketone type inhibitor can be selected from the compounds of the following formula (F4): [Chemical formula] In the formula, R 15 represents an alkyl group, a cycloalkyl group, a (cycloalkyl)alkyl group, a C6-C 10 aryl group, or a C7-C 18 arylalkyl group, and the alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl or arylalkyl group can be substituted one or more times by a chlorine, bromine or iodine atom.

[0080] According to a preferred embodiment, R 15 is a monovalent C1-C 12 , preferably a C1-C6 alkyl group (optionally substituted one or more times by a chlorine or bromine atom), or a cycloalkyl group, or a C6-C 10Represents an aryl group. The inhibitor, which is an α-acetylene ketone used according to the present invention, can be selected from the group consisting of the following compounds: 1-octyn-3-one; 8-chloro-1-octyn-3-one; 8-bromo-1-octyn-3-one; 4,4-dimethyl-1-octyn-3-one; 7-chloro-1-heptyn-3-one; 1-hexyn-3-one; 1-pentyn-3-one; 4-methyl-1-pentyn-3-one; 4,4-dimethyl-1-pentyn-3-one; 1-cyclohexyl-1-propyn-3-one; benzoacetylene and (o-chlorobenzoyl)acetylene.

[0081] The acrylonitrile-based inhibitor can be selected from the compounds of the following formula (F5):

Chemical formula

[0082] The inhibitor, which is an acrylonitrile used according to the present invention, can be selected from the group consisting of the following compounds: acrylonitrile; methacrylonitrile; 2-chloroacrylonitrile; crotononitrile and cinnamitrile.

[0083] The maleate or fumarate type inhibitor can be selected from the compounds of the following formulas (F6) and (F7):

Chemical formula

Chemical formula

[0084] According to the present invention, the term "alkenyl" is understood to mean a saturated hydrocarbon chain containing 2 to 6 carbon atoms and at least one double bond. Preferably, the alkenyl group is selected from the group consisting of vinyl and allyl. According to formulas (F6) and (F7), the term "alkoxy" is understood to mean the alkyl group as defined above bonded to an oxygen atom. The alkoxy group can be selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

[0085] According to a particular embodiment, R 18 and R 19 are, independently of one another and being the same or different, a C1-C 12 optionally substituted by a C1-C6 alkoxy group, preferably a C1-C6 alkyl group or alkenyl group.

[0086] The inhibitor which is a maleate or fumarate used according to the present invention can be selected from the group consisting of diethyl fumarate, diethyl maleate, diallyl fumarate, diallyl maleate and bis(methoxyisopropyl) maleate.

[0087] These inhibitors are added in a weight of 1 to 50000 ppm, in particular 10 to 10000 ppm, preferably 20 to 2000 ppm, even more preferably 800 ppm to 2000 ppm, based on the weight of the entire silicone composition.

[0088] The medical silicone pressure-sensitive adhesive composition of the present invention can be applied to various substrates suitable for medical use. Depending on the application field, the substrate can be a support with a very diverse range of properties.

[0089] According to a preferred embodiment, the substrate is a woven fabric, non-woven fabric, or knitted fabric, or a plastic film. The term "non-woven fabric" is understood to mean any structure made of fiber materials such as fibers, continuous filaments, or cut yarns that are formed into a net by some means and bonded by some means, excluding the entanglement of yarns, regardless of their nature or origin. Non-woven fabrics have a textile appearance, are porous, mainly composed of fibers, and are products manufactured by processes other than spinning, weaving, knitting, and knotting.

[0090] According to another preferred embodiment, the substrate is made of plastic. A wide variety of plastics may be suitable for use as the substrate according to the present invention. Examples include polyvinyl chloride, polypropylene, regenerated cellulose, polyethylene terephthalate (PET), and polyurethane, particularly melt-blown polyurethane. The substrate can be a porous soft polyurethane film or a continuous flexible polyurethane film. This flexible polyurethane film can be manufactured from melt-blown polyurethane. When the substrate is a flexible polyurethane film, the thickness is generally 5 to 600 μm, preferably 5 to 250 μm, and more preferably 10 to 100 μm.

[0091] Preferably, the substrate can be selected from paper, polyurethane, non-woven fabric, and elastic fabric.

[0092] Depending on the end use, the medical silicone pressure-sensitive adhesive composition according to the present invention can be adapted to various substrates. In particular, organopolysiloxanes A, CE, and XL can be selected so that the specific molar ratio RHAlk = tH / tAlk and the specific ratio nH XL / nH CE are more suitable for a specific substrate.

[0093] For example, when the substrate is paper, the molar ratio RHAlk = tH / tAlk can be 4.30 to 6.00, preferably 4.55 to 5.55; and / or the molar ratio nH XL / nH CE can be 0.10 to 0.22, preferably 0.12 to 0.20.

[0094] When the substrate is thermoplastic polyurethane, the molar ratio RHAlk = tH / tAlk can be 4.50 to 8.00, preferably 4.70 to 5.70; and / or the molar ratio nH XL / nH CE can be 0.50 to 11.0, preferably 1.2 to 8.0.

[0095] When the substrate is non-woven fabric, the molar ratio RHAlk = tH / tAlk can be 3.50 to 8.00, preferably 4.00 to 6.60; and / or the molar ratio nH XL / nH CE can be 1.00 to 7.50, preferably 1.20 to 6.50.

[0096] When the substrate is elastic fabric (preferably for kinesiology sports tape), the molar ratio RHAlk = tH / tAlk can be 4.10 to 8.00, preferably 5.00 to 6.60; and / or the molar ratio nH XL / nH CE can be 0.50 to 11.00, preferably 2.00 to 8.00.

[0097] Those skilled in the art can adjust the medical silicone pressure-sensitive adhesive composition according to the end use. Generally, the medical silicone pressure-sensitive adhesive composition according to the present invention can have a dynamic viscosity of 500 to 5000 mPa·s at 25°C, preferably 800 to 3000 mPa·s at 25°C, more preferably 1000 to 2500 mPa·s at 25°C.

[0098] The medical silicone pressure-sensitive adhesive composition according to the present invention can be applied or coated on various substrates by any technique well known to those skilled in the art. Examples of the application methods of the medical silicone pressure-sensitive adhesive composition of the present invention include, for example, coating techniques performed by a knife, particularly a knife over roll, a floating knife, and a knife over carpet, padding, i.e., a coating technique by squeezing between two rolls, or coating techniques by a kiss roll, a rotary machine, a reverse roll or transfer, or a spray. Other coating techniques include a curtain coating technique. Curtain coating is a process of applying a coating liquid to an article or a support. Curtain coating is characterized by the formation of a free-falling curtain of the coating liquid dropping from the lip of a hopper, and forms a coating when encountering an article moving through the curtain under the influence of gravity. This technique is widely used in the field of manufacturing multi-layer photosensitive silver supports (see, for example, U.S. Patent No. 3,508,947, U.S. Patent No. 3,508,947, and European Patent No. 537,086).

[0099] Next, the medical silicone pressure-sensitive adhesive composition coated on the substrate is crosslinked at a temperature of, for example, 100°C to 160°C, preferably 120°C to 150°C.

[0100] In this way, by crosslinking the silicone pressure-sensitive adhesive composition of the present invention, a substrate G coated with a silicone pressure-sensitive adhesive is obtained.

[0101] Embodiments of the Invention Other advantages and features of the present invention will become apparent by reading the following examples given by way of illustration and in no way limiting.

Examples

[0102] 1. Measurement Method The measurement methods implemented in the examples will be described below.

[0103] 1.1 Ease of Tearing The "ease of tearing" test is performed by cutting the cured PSA laminate into 10 cm (length) × 2.5 cm (width) strips, peeling the release liner from the PSA layer, and then quickly tearing the strip along the width. By observing the fracture location, the test results of "ease of tearing" can be classified into three levels. A = Clean fracture and no stretching line during tearing, Pass B = Difficult to break, but no stretching line during tearing, Pass C = Difficult to break and there is a stretching line during tearing, Fail

[0104] 1.2. Residue on the skin The "residue on the skin" test is performed by cutting the cured PSA laminate into 5 cm (length) × 2.5 cm (width) strips, peeling the release liner from the PSA layer, and attaching the PSA layer to the skin. After leaving it at room temperature for 4 hours, the PSA layer is peeled off, and by checking the sticking area on the skin, the test results of "residue on the skin" are classified into five levels. A = No visible adhesive and no sticky feeling when touched with fingers, Pass B = No visible adhesive and almost no sticky feeling when touched with fingers, Pass C = Visible adhesive spots, Fail D = Visible adhesive pieces, Fail E = Adhesive is visible throughout the adhesion area, Fail

[0105] 1.3. Fixing property to the substrate The "fixing property to the substrate" test is carried out by cutting the cured PSA laminate into 10 cm (length) × 2.5 cm (width) strips, peeling the release liner from the PSA layer, bending the adhesive surface and bonding both ends, and then quickly peeling it off. The test results of "fixing property to the substrate" are classified into four levels by observing the adhesion areas at both ends. A = No change in both adhesion areas, Pass B = The adhesive is damaged inside either of the adhesion areas, Pass C = An adhesive piece is peeled off from the substrate in either of the adhesion areas, Fail D = Rejection if the adhesive is completely peeled off from the substrate in any part of the subsequent area

[0106] 1.4. Peel Adhesion The "Peel Adhesion" test is carried out by cutting the cured PSA laminate into strips of 10 cm (length) × 2.5 cm (width), peeling off the release liner from the PSA layer, attaching the PSA layer to a hard paper with unevenness of 15 cm × 5 cm size, laminating it with a 2 kg rubber roller for 2 cycles, and further holding this "testable immediately" sample for 20 minutes. Then, according to FINAT FTM1, a peel test is carried out using a PA1000 - 180 peel tester of Cheminstrument Co., Ltd. The ambient conditions are 23°C and 50% RH. If the result is 4 N / 25 mm or more, it is considered qualified.

[0107] 1.5. Probe Tack Test The "Probe Tack Test" is carried out by cutting the cured PSA laminate into strips of 2.5 cm (length) × 2.5 cm (width), peeling off the release liner from the PSA layer, and performing a tack test using a PT1000 probe tack tester of Cheminstrument Co., Ltd. according to ASTM D2979. The ambient conditions are 23°C and 50% RH. If the result is 1000 g / cm 2 or more, it is considered qualified.

[0108] 1.6. Loop Tack Test The "Loop Tack Test" is carried out by cutting the cured PSA laminate into strips of 10 cm (length) × 2.5 cm (width) and peeling off the release liner from the PSA layer. The test is carried out using an LT1000 loop tack tester of Cheminstrument Co., Ltd. according to FINAT FTM9. The ambient conditions are 23°C and 50% RH. If the result is 500 g / 25 mm 2 or more, it is considered qualified.

[0109] 1.7. Re - attachment Characteristics The "re - sticking property" test is carried out using a loop tack test or a probe tack test. The tack test is repeated on the same sample until 40% of the tack is lost compared to the initial result, and the number of cycles is recorded as an indicator of the re - sticking property. The ambient conditions are 23°C and 50% RH. If the result exceeds 4, it is considered qualified.

[0110] 1.8. Peel strength The "peel strength" test is carried out by cutting the cured PSA laminate into strips of 10 cm (length) × 2.5 cm (width), peeling the release liner from the PSA layer, attaching the PSA layer to a standard fluorine release agent of 15 cm × 5 cm size, laminating it with a 2 kg rubber roller for 2 cycles, and holding this "test - ready" sample for an additional 20 minutes. Then, according to FINAT FTM3, the peel strength when peeling the PSA from the selected liner is measured by a PA1000 - 180 peel tester from Cheminstrument Co., Ltd. The ambient conditions are 23°C and 50% RH. If the result is less than 5 g / 25 mm, it is considered qualified.

[0111] 2. Preparation of the composition of the present invention 2.1. The raw materials used in the examples are shown in Table 1 below.

[0112]

Table 1

[0113] 2.2. Preparation of the "ready - to - coat" solution 37 g of organopolysiloxane resin B and 0.12 g of ECH are uniformly dissolved in 40 g of ethyl acetate, and then 23 g of organopolysiloxane A is introduced into the above - mentioned ethyl acetate solution while stirring until all components are uniformly mixed to obtain a basic composition.

[0114] Weigh 100 g of the basic composition into 50 g of ethyl acetate. Next, add crosslinking agent XL and extender CE in the amounts shown in the following table, mix uniformly, and then add catalyst D in the amount shown in the following table and mix the mixture to obtain a uniform solution called a "ready-to-use" solution, thereby obtaining the composition according to the present invention.

[0115] 3. Application to the substrate 3.1. Application Example 1, Paper Tape As a process, first coat the "ready-to-use" solution on a fluorosilicone release liner to a dry PSA thickness of 30 μm, place it in a ventilation hood for 10 minutes, and then place it in an oven at 120 °C for 5 minutes. After taking the cured layer out of the oven, cover the PSA layer with non-woven paper and laminate the resulting "sandwich" type assembly twice with a pressure of 30 psi using an autolamintor. The PSA is transferred to the required substrate side. A cured PSA laminate is obtained.

[0116] [Table 2]

[0117] Examples 5 and 6 - 8: RHAlk < 4.30 (nH XL / nH CE are the same but) results in a weak binding force (weak crosslinking) and spots remain on the skin.

[0118] Examples 12 and 2, 4: nH XL / nH CE > 0.22 (although RHAlk is the same) results in too strong a binding force, so the adhesion to the substrate is too weak and the fixing test fails.

[0119] Examples 9 - 12: nH XL / nH CE > 0.22 (regardless of the value of RHAlk) results in too strong a binding force, so the adhesion to the substrate is too weak and the fixing test fails. Moreover, unfortunately, after peeling off the PSA tape, some PSA pieces remain on the skin.

[0120] nH XL / nHCE When it is in the range of 0.10 - 0.22 for [a certain parameter] and 4.3 - 6.0 for RHAlk, it can be seen that good characteristics are obtained on the paper substrate, namely, it can be easily peeled off, has good re - sticking properties and water resistance, good fixing property to the substrate, and low skin irritation.

[0121] 3.2. Application Example 2, TPU transparent patch. As a process, a "ready - to - use" solution is coated on a TPU film (using kraft paper coated with polyethylene as a backing), dried to a PSA thickness of 30 μm, then immediately placed in an oven at 60 °C for 1 minute as soon as possible, and then placed in an oven at 120 °C for 5 minutes. After taking the cured layer out of the oven, the cured PSA layer and the silicone - fluorine release liner (Si - F liner) are laminated twice under a pressure of 30 psi. A cured PSA laminate is obtained.

[0122] [Table 3]

[0123] Examples 13 - 15: nH XL / nH CE When <0.50, the bonding strength becomes weak or it cannot be cured, and after peeling off the PSA, the bonding strength decreases and adhesive spots remain on the skin.

[0124] Examples 23 - 25: nH XL / nH CE When > 11, the bonding strength is too strong and the adhesion to the substrate becomes weak. When peeling the PSA patch from the skin, the fixing property decreases. Some adhesive pieces are transferred from the substrate to the skin.

[0125] nH XL / nH CE When it is in the range of 0.5 - 11 for [a certain parameter] and 4.5 - 8.0 for RHAlk, it can be seen that good characteristics are obtained on the TPU substrate, namely, good air permeability, good shear performance and water resistance, low irritation for long - term wearing, and good fixing property to the substrate. In particular, a PU primer is not necessary.

[0126] 3.3. Application Example 3, Non-woven Tape The substrate is a non-woven fabric.

[0127] As a process, a "ready-to-use" solution is coated on a fluorine release liner, the thickness of the dry PSA is made 36 μm, placed in a ventilation hood for 10 minutes, and then laminated twice with a non-woven fabric at a pressure of 30 psi. This sandwich-type assembly is placed in an oven at 120 °C for 5 minutes and finally taken out. The PSA is transferred to the required substrate side. A cured PSA laminate is obtained.

[0128] [Table 4]

[0129] Examples 27 - 29: nH XL / nH CE When < 1.0, the bonding force is weak, and adhesive spots remain on the skin after peeling off the PSA tape.

[0130] Examples 40 - 41: nH XL / nH CE When > 7.5, the peeling force from the liner is too high and the bonding force is too strong, causing poor fixing property to the substrate (since the adhesive force to the substrate is weak, PSA pieces remain on the skin).

[0131] nH XL / nH CE When nH is in the range of 1.00 - 7.50 and RHAlk is in the range of 3.5 - 8.0, it can be seen that good properties are obtained on the non-woven fabric substrate, namely, good air permeability, good shear performance and water resistance, and good fixing property to the substrate.

[0132] 3.4. Application Example 4, Elastic Fabric Tape The same process as in Application Example 3 is carried out to obtain a cured PSA laminate. The substrate is an elastic fabric substrate such as cotton or nylon.

[0133] [Table 5]

[0134] Examples 45 and 46, Examples 47 and 48: When RHAlk < 4.10, the bonding force is weak, and adhesive spots remain on the skin after peeling off the PSA tape.

[0135] Examples 42 and 44, Examples 43 and 46: nH XL / nH CE When < 0.50, the bonding force is weak, and adhesive spots remain on the skin after peeling off the PSA tape.

[0136] nH XL / nH CE It can be seen that when nH is in the range of 0.5 to 11 and RHAlk is in the range of 4.1 to 8.0, good characteristics can be obtained in the elastic fabric substrate, that is, excellent sweat resistance, repositionability, air permeability, and low irritation suitable for long-term wearing.

Claims

1. A medical silicone pressure-sensitive adhesive composition comprising the following: ・ At least one organopolysiloxane A containing at least two C 2 to C 6 alkenyl radicals each bonded to a silicon atom, ・ At least one organopolysiloxane resin B containing a hydroxyl group bonded to a silicon atom, ・ At least one organopolysiloxane crosslinking agent XL having at least three hydrogen atoms bonded to a silicon atom, ・ At least one organopolysiloxane extender CE having exactly two terminal hydrogen atoms bonded to a silicon atom, ・ At least one hydrosilylation catalyst D, ・ At least one solvent E, ・ At least one hydrosilylation inhibitor F; Here, The composition is to be coated on any one of paper, polyurethane, non-woven fabric, and elastic fabric, When the composition is to be coated on paper, organopolysiloxane A, CE, and XL are selected such that the molar ratio RHA lk = tH / tAlk is 4.30 to 6.00, and nH XL / nH CE is 0.10 to 0.22, When the composition is to be coated on polyurethane, organopolysiloxane A, CE, and XL are selected such that the molar ratio RHA lk = tH / tAlk is 4.50 to 8.00, and the molar ratio nH XL / nH CE is 0.50 to 11.0, When the composition is to be coated on non-woven fabric, organopolysiloxane A, CE, and XL are selected such that the molar ratio RHA lk = tH / tAlk is 3.50 to 8.00, and the molar ratio nH XL / nH CE is 1.00 to 7.50, or When the composition is coated on an elastic fabric, organopolysiloxanes A, CE, and XL are selected such that the molar ratio RHA lk = tH / tAlk is 4.10 to 8.00, and the molar ratio nH XL / nH CE is 0.50 to 11.00, where: · tH = the number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxanes XL and CE, · tAlk = the number of moles of alkenyl directly bonded to the silicon atoms of organopolysiloxane A, · nH XL = the number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane XL, · nH CE = the number of moles of hydrogen atoms directly bonded to the silicon atoms of organopolysiloxane CE.

2. Organopolysiloxane A is an organopolysiloxane gum having a viscosity of 200 mm / 10 to 2000 mm / 10 at 25°C, and / or an organopolysiloxane gum having a viscosity exceeding 600000 mPa·s at 25°C, and / or an organopolysiloxane gum having an alkenyl content of 0.001% by weight to 0.5% by weight based on the total weight of organopolysiloxane A, the composition according to Claim 1.

3. When the composition is coated on paper, the molar ratio RHA lk = tH / tAlk is 4.55 to 5.55, and the molar ratio nH XL / nH CE is 0.12 to 0.20, the composition according to Claim 1 or 2.

4. When the composition is coated on polyurethane, the molar ratio RHA lk = tH / tAlk is 4.70 to 5.70, and the molar ratio nH XL / nH CE is 1.2 to 8.0, the composition according to Claim 1 or 2.

5. When the composition is coated on a nonwoven fabric, the molar ratio RHA lk = tH / tAlk is 4.00 to 6.60, and the molar ratio nH XL / nH CE is 1.20 to 6.

50. The composition according to claim 1 or 2.

6. When the composition is coated on an elastic fabric, the molar ratio RHA lk = tH / tAlk is 5.00 to 6.60, and the molar ratio nH XL / nH CE is 2.00 to 8.

00. The composition according to claim 1 or 2.

7. The organopolysiloxane crosslinking agent XL has a dynamic viscosity of 40 to 1000 mPa·s at 25°C, and / or the organopolysiloxane extender CE has a dynamic viscosity of 1 to 1000 mPa·s at 25°C. The composition according to any one of claims 1 to 6.

8. The organopolysiloxane resin B is an MQ (OH) , MQQ (OH) or MM Vi Q (OH) type of silicone hydroxide resin, contains 0.1 to 4% by weight of hydroxyl groups based on the dry weight of the organopolysiloxane resin B, and / or the ratio of M units to Q units is 0.5 to 1.

2. The composition according to any one of claims 1 to 7.

9. The weight ratio of the organopolysiloxane resin B to the organopolysiloxane A is 0.8 to 2.

5. The composition according to any one of claims 1 to 8.

10. A method for coating a substrate using the composition according to any one of claims 1 to 9.

11. A coated substrate obtained by using the method according to claim 10.

12. A substrate coated with a silicone pressure-sensitive adhesive obtained by crosslinking the medical silicone pressure-sensitive adhesive composition according to any one of claims 1 to 9.

13. A skin patch article comprising a substrate having a silicone pressure-sensitive adhesive obtained by crosslinking the medical silicone pressure-sensitive adhesive composition according to any one of Claims 1 to 9 continuously or discontinuously applied to at least one of both surfaces.

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