Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
  • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
  • A61F13/00—Bandages or dressings; Absorbent pads
  • A61F13/02—Adhesive bandages or dressings
  • A61F13/0246—Adhesive bandages or dressings characterised by the skin-adhering layer
  • A61F13/0253—Adhesive bandages or dressings characterised by the skin-adhering layer characterized by the adhesive material
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
  • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
  • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
  • A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
  • A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
  • A61K9/7038—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer
  • A61K9/7046—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds
  • A61K9/7069—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. polysiloxane, polyesters, polyurethane, polyethylene oxide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2483/00—Presence of polysiloxane

Definitions

• the present invention relates to an addition-curable silicone pressure-sensitive adhesive composition for application to the skin and an adhesive tape for application to the skin using a cured product of the composition.
• the polysiloxane constituting the silicone pressure-sensitive adhesive has a main skeleton composed of Si—O bonds having high binding energy, it is excellent in heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. For this reason, they are used in severe environments such as heat-resistant tapes, electric insulating tapes, process masking tapes, and mica tapes having flame retardancy. Silicone pressure-sensitive adhesives are used for application to the skin because of their breathability and low irritation.
• Acrylic and rubber adhesives are often used for skin application.
• these adhesives have an excessively high adhesive force to an adherend such as the skin, so that the exfoliation of the skin is excessively exfoliated at the time of exfoliation, or the body hair is pulled, causing pain and discomfort, and further to the skin. Excessive irritation may cause secondary inflammation.
• silicone adhesives have a feature that they are less likely to peel off the hair and the stratum corneum at the time of peeling, but the adhesive strength is reduced when they are reapplied after peeling. There is.
• silicone adhesives are used for medical tapes such as surgical tapes and dressing materials. In such applications, there is a temporary peeling for re-applying or observation, and the adhesive strength may not be reduced by re-applying. Not desirable.
• the present invention has been made in view of the above circumstances, and has an appropriate adhesive strength to human skin, has a small decrease in adhesive strength when re-applied, and has an excellent reworkability and an adhesive layer exhibiting durability.
• An object of the present invention is to provide an addition reaction-curable silicone pressure-sensitive adhesive composition for skin application and a pressure-sensitive adhesive tape for skin application using a cured product of the composition.
• the present invention provides an addition-curable silicone pressure-sensitive adhesive composition for application to the skin, comprising the following components (X), (C) and (D).
• (X) A mixture of the following components (A) and (B) or a condensation reaction product of the following components (A) and (B): 100 parts by mass
• (A) The following components (A1) and (A2) A) a diorganopolysiloxane having a mass ratio of (A1) / (A2) in the range of 90/10 to 15/85: 55 to 90 parts by mass;
• A1 a diorganopolysiloxane having two or more alkenyl groups in one molecule and having an alkenyl group content of 0.0005 mol / 100 g or more and less than 0.15 mol / 100 g;
• (A2) a diorganopolysiloxane having a terminal SiOH group and no alkenyl group;
• R 1 3 SiO 0.5 units R 1 is a monovalent hydrocarbon
• the addition-curable silicone pressure-sensitive adhesive composition for application to the skin of the present invention has an appropriate adhesive strength to human skin, has a small decrease in adhesive strength when reapplied, and has excellent reworkability and durability.
• the indicated pressure-sensitive adhesive layer can be provided.
• the composition further contains the following component (E).
• the concentration and viscosity of the addition-curable silicone pressure-sensitive adhesive composition for application to the skin of the present invention can be made favorable.
• the component (C) is preferably an organohydrogenpolysiloxane represented by the following formula (1).
• R 2 is the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, a is an integer of 0 or more, b is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, e is an integer of 0 or more, f is an integer of 0 or more, a + b ⁇ 3, and 3 ⁇ a + b + c + d + e + f ⁇ 1,000.)
• the mass ratio of (A1) / (A2) in the component (A) is in the range of 75/25 to 25/75.
• the component (X) is a condensation reaction product of the component (A1), the component (A2), and the component (B), or the component (A2) and the component (B). It is preferably a mixture of the condensation reaction product and the component (A1).
• the addition reaction control agent is contained as the component (F) in an amount of 0.05 to 8 parts by mass based on 100 parts by mass of the total of the components (A) and (B).
• the treatment liquid containing the silicone pressure-sensitive adhesive composition may be thickened or gelled. Can be prevented.
• the present invention is a pressure-sensitive adhesive tape for skin application having a substrate and a cured product layer laminated on at least one surface of the substrate, wherein the cured product layer is a cured product of the silicone pressure-sensitive adhesive composition. And a pressure-sensitive adhesive tape for adhering to skin.
• the cured product layer is made of a cured product of the silicone pressure-sensitive adhesive composition, it has a moderate adhesive strength to human skin and fixes the base material to the skin. In addition, the adhesive strength at the time of reattachment is small, and reworkability and durability are excellent.
• the present invention also provides a method for using the pressure-sensitive adhesive tape for applying the skin to the skin, wherein the pressure-sensitive adhesive tape is applied to the skin.
• the adhesive tape for applying skin can be used gently on human skin.
• the addition reaction-curable silicone pressure-sensitive adhesive composition for application to the skin of the present invention has an appropriate adhesive strength to human skin, so that the substrate can be fixed to the skin. Furthermore, it is possible to provide a pressure-sensitive adhesive tape for skin application that has a small decrease in adhesive strength when re-applied and has excellent reworkability and durability.
• the present inventors have conducted intensive studies on the above problems, and as a result, have found that a diorganopolysiloxane composed of specific components (A1) and (A2) and having a mass ratio of (A1) / (A2) within a specific range.
• A component, a component (B) comprising a specific organopolysiloxane, a component comprising an organohydrogenpolysiloxane, and a platinum group metal-based catalyst component;
• the silicone adhesive becomes soft and has cohesive force, and reworkability is obtained.
• the inventors have found that the present invention can be performed and completed the present invention.
• the present invention is an addition-curable silicone pressure-sensitive adhesive composition for application to the skin, comprising the following components (X), (C) and (D).
• (X) A mixture of the following components (A) and (B) or a condensation reaction product of the following components (A) and (B): 100 parts by mass
• (A) The following components (A1) and (A2) A) a diorganopolysiloxane having a mass ratio of (A1) / (A2) in the range of 90/10 to 15/85: 55 to 90 parts by mass;
• A1 a diorganopolysiloxane having two or more alkenyl groups in one molecule and having an alkenyl group content of 0.0005 mol / 100 g or more and less than 0.15 mol / 100 g;
• (A2) a diorganopolysiloxane having a terminal SiOH group and no alkenyl group;
• R 1 3 SiO 0.5 units R 1 is a monovalent hydrocarbon group having
• the “addition reaction-curable silicone pressure-sensitive adhesive composition for application to the skin” may be simply referred to as “silicone pressure-sensitive adhesive composition”.
• the silicone pressure-sensitive adhesive composition of the present invention is an addition-curable silicone pressure-sensitive adhesive composition for application to the skin, which contains the following components (X), (C) and (D) as essential components.
• (X) A mixture of the following components (A) and (B) or a condensation reaction product of the following components (A) and (B): 100 parts by mass
• (A) The following components (A1) and (A2) A) a diorganopolysiloxane having a mass ratio of (A1) / (A2) in the range of 90/10 to 15/85: 55 to 90 parts by mass;
• (A2) a diorganopolysiloxane having a terminal SiOH group and no alkenyl group;
• (B) R 1 3 Si
• the silicone pressure-sensitive adhesive composition of the present invention contains, in addition to the above components, component (E) which is an aliphatic hydrocarbon solvent, component (F) which is an addition reaction control agent, and other optional components, if necessary. be able to.
• component (E) which is an aliphatic hydrocarbon solvent
• component (F) which is an addition reaction control agent
• other optional components if necessary. be able to.
• the addition-curable silicone pressure-sensitive adhesive composition for application to the skin of the present invention is a mixture of the components (A) and (B) or a condensation reaction product of the components (A) and (B).
• the condensation reaction product may include a reaction product in which the component (A) and the component (B) are partially condensed, and may include an excess component of the component (A) and the component (B). There is. Further, it may contain an unreacted product of the component (A) and the component (B). Further, the component (A) is composed of the components (A1) and (A2).
• the mixture of the components (A) and (B) is a mixture of the components (A1), (A2) and (B), and the condensation reaction product of the components (A) and (B) is represented by ( It is a product obtained by a condensation reaction between component (A) and component (B).
• the condensation reaction product may include a reaction product in which the component (A1) and / or the component (A2) and the component (B) are partially condensed, and the component (A1), the component (A2) ) And unreacted components of component (B).
• the component (A) (the components (A1) and (A2)), the component (B), a mixture thereof, and a condensation reaction product will be described.
• the component (A) is (A1) a diorganopolysiloxane having two or more alkenyl groups in one molecule and having an alkenyl group content of 0.0005 mol / 100 g or more and less than 0.15 mol / 100 g, and (A2) a diorganopolysiloxane having a SiOH group at an end and having no alkenyl group, a diorganopolysiloxane having a mass ratio of (A1) / (A2) in the range of 90/10 to 15/85. It is.
• the mass ratio of (A1) / (A2) is preferably from 80/20 to 20/80, and more preferably from 75/25 to 25/75.
• the component (A1) is a diorganopolysiloxane having two or more alkenyl groups in one molecule and having an alkenyl group content of 0.0005 mol / 100 g or more and less than 0.15 mol / 100 g.
• the component (A1) may be a diorganopolysiloxane in which the molecular chain ends are not completely blocked (that is, some SiOH groups remain), and may be used alone or in combination of two or more. May be used in combination. For example, one represented by the following formula (2) can be exemplified.
• R 3 is the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least two of R 3 include an alkenyl group-containing organic group having 2 to 10 carbon atoms.
• G is 2 Or more integers, h is an integer of 1 or more, i is an integer of 0 or more, j is an integer of 0 or more, and 100 ⁇ g + h + i + j ⁇ 20,000.
• R 3 is the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least two of R 3 include an alkenyl group-containing organic group having 2 to 10 carbon atoms.
• the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl group such as a phenyl group.
• Some or all of the hydrogen atoms bonded to the carbon atoms of the group may be substituted with halogen atoms or other groups, and examples of the substituent include a trifluoromethyl group and a 3,3,3-trifluoropropyl group. Is exemplified. Among them, a saturated aliphatic group or aromatic group is preferable, and a methyl group and a phenyl group are preferable.
• R 3 contains a phenyl group
• the content of the phenyl group is preferably from 0.1 to 30 mol% of all organic groups bonded to silicon atoms of the diorganopolysiloxane of the formula (2). When the content is within this range, the resulting silicone pressure-sensitive adhesive layer has a preferable adhesive strength to human skin.
• the alkenyl group-containing organic group is preferably an organic group having 2 to 10 carbon atoms.
• alkenyloxyalkyl groups such as a methacryloylalkyl group and a cyclohexenylethyl group; and alkenyloxyalkyl groups such as a vinyloxypropyl group.
• a vinyl group is preferred from an industrial viewpoint.
• the amount of the alkenyl group contained in the component (A1) is at least 0.0005 mol and less than 0.15 mol, preferably 0.0007 to 0.13 mol, more preferably 0.001 to 0.1 mol per 100 g of the organopolysiloxane. 0.10 mol is more preferred. If the amount is less than 0.0005 mol, the curability may decrease or the holding power may decrease. On the other hand, if the amount is 0.15 mol or more, the obtained pressure-sensitive adhesive layer becomes hard, and it is not possible to obtain a film having appropriate adhesive strength and tack.
• the measurement of the amount of the alkenyl group can be usually determined by the Hanus method using iodine bromide (the same applies hereinafter).
• g in the formula (2) is an integer of 2 or more
• h is an integer of 1 or more
• i is an integer of 0 or more
• j is 0
• g + h + i + j is 100 or more, the reactivity does not decrease without excessively increasing the number of crosslinking points.
• the molecular weight is 20,000 or less, the composition is easily stirred and mixed without extremely increasing the viscosity of the composition, so that the workability is good.
• the component (A1) can be produced by subjecting a cyclic low-molecular siloxane such as octamethylcyclotetrasiloxane to ring-opening polymerization using a catalyst.
• a cyclic low-molecular siloxane such as octamethylcyclotetrasiloxane
• a catalyst for ring-opening polymerization
• a cyclic low-molecular siloxane as a raw material is contained. Therefore, it is preferable to use a product obtained by distilling this under heating and reduced pressure while passing an inert gas through the reaction product.
• the amount of hydroxyl groups (SiOH groups) bonded to silicon atoms contained in the component (A1) is preferably 0 to 0.45% by mass, particularly preferably 0 to 0.40% by mass in the component (A).
• the measurement of the amount of SiOH groups can be usually determined by a known method such as a Grignard method or an NMR method (the same applies hereinafter).
• the property of the diorganopolysiloxane of the component (A1) may be oily or raw rubber.
• the viscosity of the component (A1) at 25 ° C. is preferably from 1,000 to 1,000,000 mPa ⁇ s, particularly preferably from 5,000 to 800,000 mPa ⁇ s, if it is oily.
• the viscosity of the solution dissolved in toluene is preferably from 1,000 to 100,000 mPa ⁇ s, and particularly preferably from 3,000 to 80,000 mPa ⁇ s, so as to have a concentration of 30% by mass.
• the viscosity is not less than the lower limit, the curability of the pressure-sensitive adhesive composition is not reduced, and the holding power is not reduced. If the viscosity is not more than the upper limit, the pressure-sensitive adhesive composition does not become too high in viscosity. This is preferred because stirring during the production of the composition is facilitated.
• the viscosity is a value measured at 25 ° C. using a BM-type rotational viscometer (the same applies hereinafter).
• one type may be used alone, or two or more types may be used in combination.
• component (A1) examples include, but are not limited to, the following.
• Me, Vi, and Ph in the following formulas represent a methyl group, a vinyl group, and a phenyl group, respectively.
• (100 ⁇ z1 ⁇ 5,000) (100 ⁇ z2 ⁇ 15,000) (100 ⁇ z3 ⁇ 19,998, 2 ⁇ z4 ⁇ 2,000, 102 ⁇ z3 + z4 ⁇ 20,000) (100 ⁇ z5 ⁇ 19,998, 2 ⁇ z6 ⁇ 2,000, 102 ⁇ z5 + z6 ⁇ 20,000) (100 ⁇ z7 ⁇ 19,999, 1 ⁇ z8 ⁇ 2,000, 101 ⁇ z7 + z8 ⁇ 20,000)
• the component (A2) is a diorganopolysiloxane having a terminal SiOH group and no alkenyl group, and examples thereof include those represented by the following formula (3).
• R 4 is independently of each other a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group having no aliphatic unsaturated bond, and at least two of R 4 include a hydroxyl group. Is an integer of 2 or more, l is an integer of 1 or more, m is an integer of 0 or more, n is an integer of 0 or more, and 100 ⁇ k + 1 + m + n ⁇ 20,000.)
• the R 4 independently of one another if not a hydroxyl group, an aliphatic unsaturated bond 1 to 10 carbon atoms that does not have, is preferably a monovalent hydrocarbon group having 1 to 8 as R 4 Is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, and a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable. Is preferred.
• the content of the phenyl group is preferably 0.1 to 30 mol% of all organic groups bonded to silicon atoms of the diorganopolysiloxane of the formula (4).
• the content is 0.1 to 30 mol%, the resulting silicone pressure-sensitive adhesive layer has favorable pressure-sensitive adhesive properties (tack, tackiness), and the suitability of the pressure-sensitive adhesive for skin application is improved.
• k in the formula (3) is an integer of 2 or more
• l is an integer of 1 or more
• m is an integer of 0 or more
• n is 0
• k + l + m + n is 100 or more, uniform application becomes easy without the viscosity of the composition becoming very low. If the molecular weight is 20,000 or less, the viscosity of the composition is not too high and the composition is easily stirred and mixed, so that the workability is improved.
• the property of the diorganopolysiloxane of the component (A2) may be oily or raw rubber.
• the viscosity of the component (A2) at 25 ° C. is preferably from 300 to 1,000,000 mPa ⁇ s, particularly preferably from 3,000 to 80,000 mPa ⁇ s, if it is oily.
• the viscosity is not less than the lower limit, uniform application becomes easy, and when the viscosity is not more than the upper limit, the viscosity of the pressure-sensitive adhesive composition does not become too high, so that stirring when producing the composition becomes easy.
• the amount of the SiOH group in the component (A2) is preferably 0.002 to 0.45% by mass, more preferably 0.005 to 0.4% by mass in the component (A2).
• one type may be used alone, or two or more types may be used in combination.
• component (A2) include, but are not limited to, the following.
• Me and Ph in the following formulas represent a methyl group and a phenyl group, respectively. (100 ⁇ z12 ⁇ 5,000) (100 ⁇ z13 ⁇ 19,999, 1 ⁇ z14 ⁇ 2,000, 101 ⁇ z13 + z14 ⁇ 20,000)
• R 1 3 SiO 0.5 units (R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently.), A SiO 2 units, a hydroxyl group bonded to a silicon atom containing siloxane units having the siloxane units and / or silicon atom-bonded alkoxy group having 1 to 6 carbon atoms having, R 1 3 molar ratio of SiO 0.5 units / SiO 2 units is 0.5 to 1 0.5, preferably 0.6 to 1.3. When the molar ratio is less than 0.5, the adhesive strength and tack of the obtained silicone pressure-sensitive adhesive layer decrease. When the molar ratio exceeds 1.5, the adhesive strength and holding power of the obtained silicone pressure-sensitive adhesive layer decrease.
• R 1 is a monovalent hydrocarbon group having 1 to 10, preferably 1 to 8 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group; a cycloalkyl group such as a cyclohexyl group; An alkyl group; an aryl group such as a phenyl group; an alkenyl group such as a vinyl group, an allyl group, and a hexenyl group, and a methyl group is preferable.
• the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.
• component but it is an essential R 1 3 SiO 0.5 units and SiO 2 units, optionally R 1 SiO 1.5 units and R 1 2 SiO units (R 1 is One or both of the above) may be contained in the component (B).
• the total content of R 1 3 SiO 0.5 units and SiO 2 units is not particularly limited, (B) the total siloxane units of component, preferably 80 to 100 mol%, More preferably, it is 90 to 100 mol%.
• the component (B) includes a siloxane unit having a hydroxyl group bonded to a silicon atom (silanol group-containing unit) and / or a siloxane unit having an alkoxy group having 1 to 6 carbon atoms bonded to a silicon atom (alkoxy group-containing unit).
• the amount of these silanol group-containing units is preferably such that the hydroxyl group content is 0.1 to 5% by mass, preferably 0.2 to 4% by mass of the component (B). When the hydroxyl group content is 5% by mass or less, the tackiness and curability of the obtained silicone pressure-sensitive adhesive layer do not decrease.
• the amount of the alkoxy group-containing unit is preferably such that the content of the alkoxy group becomes 10% by mass or less, preferably 8% by mass or less of the component (B).
• the alkoxy group content is 10% by mass or less, tackiness and curability of the obtained silicone pressure-sensitive adhesive layer do not decrease.
• the total amount of the silanol group-containing unit and the alkoxy group-containing unit is 0.1 to 12% by mass, particularly 0.2 to 10% by mass of the component (B), as the sum of the hydroxyl group content and the alkoxy group content. %.
• the silanol group-containing units, R 1 2 (HO) SiO 0.5 units, R 1 (HO) 2 SiO 0.5 units, R 1 (HO) SiO units can be exemplified such as (HO) SiO 1.5 units.
• R 1 2 (R'O) SiO 0.5 units R 1 (R'O) 2 SiO 0.5 units
• R 1 (R'O) SiO units R'O) SiO 1.5
• R'O is independently an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, and a propoxy group).
• the component (B) preferably has a weight average molecular weight of 500 to 10,000, more preferably 1,000 to 8,000.
• the weight average molecular weight can be generally determined as a polystyrene equivalent weight average molecular weight in gel permeation chromatography (GPC) analysis using toluene as a developing solvent (the same applies hereinafter).
• the component (B) may be used alone or in combination of two or more.
• the addition-curable silicone pressure-sensitive adhesive composition for application to the skin of the present invention can contain a mixture of the components (A) and (B) as the component (X).
• the mixture of component (A) and component (B) can be a simple mixture of components (A1), (A2) and (B).
• the means for obtaining the mixture is not particularly limited.
• the compounding ratio is lower than 55/45, the adhesive strength at the time of re-attachment is reduced. On the other hand, if the compounding ratio exceeds 90/10, the adhesive strength of the obtained adhesive layer becomes insufficient.
• the addition-curable silicone pressure-sensitive adhesive composition for application to the skin of the present invention can contain, as the component (X), a condensation reaction product of the components (A) and (B).
• the condensation reaction product is not particularly limited as long as it is a product of a condensation reaction between the component (A) and the component (B).
• the condensation reaction product may include a reaction product in which the component (A) and the component (B) are partially condensed, and may include an excess component of the component (A) and the component (B). Further, it may contain an unreacted product of the component (A) and the component (B).
• the component (X) is a condensation reaction product of the component (A1), the component (A2) and the component (B), or a mixture of the condensation reaction product of the component (A2) and the component (B) and the component (A1).
• the condensation reaction product may include a reaction product in which the component (A1) and / or the component (A2) and the component (B) are partially condensed, and the component (A1), the component (A2) ) And unreacted components of component (B).
• the component (A1) has a functional group capable of performing a condensation reaction
• it may be a condensation reaction product of the component (A1), the component (A2), and the component (B).
• a “condensation reaction product of the component (A1), the component (A2) and the component (B), or a mixture of the condensation reaction product of the component (A2) and the component (B) and the component (A1)” Is also referred to as “(AB) component”.
• the mixing ratio of the components (A) and (B) and the mass ratio of (A1) / (A2) in the component (AB) are the same as in the case of the mixture of the components (A) and (B).
• the condensation reaction of the component (A) and the component (B) can be performed simultaneously or sequentially.
• the condensation reaction product the hydroxyl group of the component (A1) or (A2) and the alkoxy group or the hydroxyl group of the component (B) may be subjected to a hydrolysis condensation reaction or a condensation reaction together to form a condensation reaction product
• a component obtained by subjecting the component (A2) and the component (B) to a hydrolysis-condensation reaction or a condensation reaction and condensing the component (A1) may be used.
• a mixture of the components (A1), (A2) and (B) dissolved in a solvent such as toluene is reacted at room temperature (25 ° C.) or under reflux with heating using an alkaline catalyst. It may be neutralized accordingly.
• a solvent such as toluene
• examples of the alkaline catalyst used in the above reaction include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; sodium hydrogen carbonate and hydrogen carbonate Bicarbonates such as potassium; metal alkoxides such as sodium methoxide and potassium butoxide; organic metals such as butyllithium; potassium silanolate; ammonia gas, aqueous ammonia, nitrogen compounds such as methylamine, trimethylamine, and triethylamine. , Ammonia gas or aqueous ammonia is preferred.
• metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide
• carbonates such as sodium carbonate and potassium carbonate
• sodium hydrogen carbonate and hydrogen carbonate Bicarbonates such as potassium
• metal alkoxides such as sodium methoxide and potassium butoxide
• organic metals such as butyllithium
• potassium silanolate such as ammonia gas,
• the temperature of the condensation reaction can be from 10 to 150 ° C., but it is usually from room temperature (25 ° C.) to the reflux temperature of the organic solvent.
• the reaction time is not particularly limited, but may be 0.5 to 20 hours, preferably 1 to 16 hours.
• a neutralizing agent for neutralizing the alkaline catalyst may be added.
• the neutralizing agent include acidic gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid, and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid.
• an inert gas such as nitrogen may be passed through to distill off.
• the component (C) is an organohydrogenpolysiloxane containing three or more Si—H groups in one molecule, and can be used alone or in an appropriate combination of two or more.
• the number of Si—H groups in one molecule is 3 or more, preferably 5 to 1,000, more preferably 8 to 500.
• the organohydrogenpolysiloxane of the component (C) may be linear, branched or cyclic. This organohydrogenpolysiloxane preferably has a viscosity at 25 ° C. of 1 to 5,000 mPa ⁇ s, more preferably 2 to 3,000 mPa ⁇ s.
• organohydrogenpolysiloxane of the component (C) examples include those represented by the following formula (1).
• R 2 is the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, a is an integer of 0 or more, b is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, e is an integer of 0 or more, f is an integer of 0 or more, a + b ⁇ 3, and 3 ⁇ a + b + c + d + e + f ⁇ 1,000.)
• R 2 is identical or different, aliphatic unsaturated bond 1 to 10 carbon atoms that does not have, is preferably a monovalent hydrocarbon group having 1 to 8, as R 2 include a methyl group, ethyl Groups, alkyl groups such as propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group and tolyl group. Further, some or all of the hydrogen atoms bonded to carbon atoms of these groups may be substituted with halogen atoms or other groups, and examples of the substituent include a trifluoromethyl group, Examples thereof include a fluoropropyl group. Among them, a saturated aliphatic group or aromatic group is preferable, and a methyl group or a phenyl group is more preferable. Particularly, a methyl group is preferable.
• a is an integer of 0 or more
• b is an integer of 1 or more
• c is an integer of 0 or more
• d is an integer of 0 or more
• e is an integer of 0 or more
• f is an integer of 0 or more
• a + b ⁇ 3 ⁇ a + b + c + d + e + f ⁇ 1,000, preferably 5 ⁇ a + b + c + d + e + f ⁇ 1,000.
• component (C) examples include, but are not limited to, the following.
• Me and Ph in the following formulas represent a methyl group and a phenyl group, respectively. (3 ⁇ z15 ⁇ 1,000) (3 ⁇ z16 ⁇ 999, 1 ⁇ z17 ⁇ 997, 4 ⁇ z16 + z17 ⁇ 1,000) (1 ⁇ z18 ⁇ 999, 1 ⁇ z19 ⁇ 999, 2 ⁇ z18 + z19 ⁇ 1,000)
• the molar ratio of the Si—H group in the component (C) to the alkenyl group in the component (A) (Si—H group in the component (C) / (A) in the component (A)) (Alkenyl group) is from 0.2 to 15, more preferably from 0.5 to 8.5, even more preferably from 0.8 to 7.0.
• the molar ratio is less than 0.2, the crosslink density becomes low, and there is a possibility that the cohesive strength and the holding power become low.
• it exceeds 15 the crosslink density becomes too high, and an appropriate adhesive force and tack to the skin may not be obtained.
• silicone adhesives Compared to acrylic or rubber-based adhesives, silicone adhesives have a feature that they are less likely to peel the hair and the stratum corneum at the time of peeling, but there is a problem that the adhesive strength decreases when they are reapplied after peeling. . This is presumably because the adhesive surface is contaminated with keratin and body hair, and a component that inhibits adhesion remains between the adhesive surface and the skin when re-applied, resulting in a decrease in adhesive force.
• the hardness of the pressure-sensitive adhesive affects the reworkability of the pressure-sensitive adhesive obtained from the usual addition reaction-curable silicone pressure-sensitive adhesive composition. If the pressure-sensitive adhesive layer is soft, the pressure-sensitive adhesive layer is deformed when the pressure-sensitive adhesive tape is peeled off the skin, and the lifting of the skin is suppressed. As a result, the surface of the pressure-sensitive adhesive is not contaminated by keratin or body hair, and the adhesive strength does not decrease when re-applied.
• the silicone adhesive becomes soft and has cohesive strength, and reworkability is obtained. be able to. Furthermore, since the adhesive is soft, it easily follows the uneven structure of the skin, and thus has excellent skin wettability.
• the molar ratio (SiH group / SiOH) of the total amount of SiH groups to the total amount of SiOH groups in the composition is preferably from 0.02 to 200,000, particularly preferably from 0.1 to 100,000.
• the molar ratio of the total amount of SiH groups to the amount of SiOH groups (SiH group / SiOH group) is 0. It is preferably from 0.05 to 200,000, particularly preferably from 0.1 to 100,000.
• the component (D) is a platinum group metal-based catalyst and can be used alone or in combination of two or more.
• the platinum group metal-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reactant of chloroplatinic acid and an alcohol, a reactant of chloroplatinic acid and an olefin compound, and a chloroplatinic acid and a vinyl-containing siloxane.
• Examples include a reactant, a platinum-based catalyst such as a complex of platinum and a vinyl group-containing siloxane, and a catalyst containing a metal such as ruthenium, rhodium, palladium, and iridium. In the present invention, among these, a platinum catalyst is preferable.
• Component (D) is added in an amount of 1 to 5,000 ppm, preferably 5 to 500 ppm, more preferably 10 to 200 ppm, as platinum group metal, based on the total weight of components (A) and (B). . If it is less than 1 ppm, the curability is reduced, the crosslinking density is reduced, and the holding power is reduced. If it exceeds 5,000 ppm, the usable time of the treatment bath is shortened.
• the catalyst of the component (D) is often not mixed in the silicone pressure-sensitive adhesive.
• the component (D) can be uniformly mixed and used before actual use. . It is desirable to add the component (D) immediately before use in terms of pot life.
• the component (E) is an aliphatic hydrocarbon solvent other than the aromatic hydrocarbon solvent, and examples thereof include those which uniformly dissolve the components (A) and (B) described above. Specific examples thereof include aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin (boiling point: 115 to 138 ° C.), or a mixed solvent thereof. Does not contain aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and styrene.
• aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and styrene.
• the amount of the component (E) is not particularly limited, but is preferably 25 to 900 parts by mass, more preferably 50 to 500 parts by mass, and more preferably 60 to 300 parts by mass, per 100 parts by mass of the total of the components (A) and (B). Parts by mass are more preferred.
• the component (F) is an addition reaction controlling agent, and can be used alone or in combination of two or more.
• the addition reaction control agent is used before the heat curing, for example, during the preparation of the silicone pressure-sensitive adhesive composition or during the application of the silicone pressure-sensitive adhesive composition to the substrate, the treatment liquid containing the silicone pressure-sensitive adhesive composition increases the viscosity.
• it is an optional component that can be added to prevent gelation from occurring.
• component (F) include: 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and the like.
• the compounding amount of the component (F) is in the range of 0 to 8 parts by mass, preferably 0.05 to 8 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). More preferably, it is in the range of 0.1 to 5 parts by mass. When the blending amount of the component (F) is at most 8 parts by mass, the curability of the obtained composition will not be reduced.
• optional ingredients can be added in addition to the above components.
• non-reactive organopolysiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane; phenol-based, quinone-based, amine-based, phosphorus-based, phosphite-based, sulfur-based, and thioether-based antioxidants; Benzophenone-based light stabilizers; Phosphate ester-based, halogen-based, phosphorus-based, antimony-based flame retardants; Cationic activators, anionic activators, nonionic activators, and other antistatic agents;
• aromatic hydrocarbon solvents such as toluene, xylene, hexane, heptane, octane, isooctane, decane, aliphatic hydrocarbon solvents such as cyclo
• the silicone pressure-sensitive adhesive composition of the present invention can be obtained by mixing the components (A) to (D), and if necessary, the components (E), (F) and other components.
• the order of mixing the components is not particularly limited.
• the component (A) obtained by subjecting the components (A) and (B) to a condensation reaction can be used instead of the component (A) and the component (B).
• the component (AB) can be obtained, for example, as follows. A solution composed of the component (A1), the component (A2), the component (B) and, if necessary, the component (E) (solvent) and an alkaline catalyst (aqueous ammonia, etc.) is stirred at room temperature to mix the components (A2) and (B). ) To obtain a condensation reaction product of the components The mixture is further heated under reflux to obtain a reaction product (a mixture of a condensation reaction product of the component (A2) and the component (B) and the component (A1)).
• the component (F) and the component (E) are added to the component (A) and the component (B) or the component (AB) and mixed to synthesize a silicone pressure-sensitive adhesive base composition.
• the silicone pressure-sensitive adhesive composition is prepared by mixing the component (C) and the component (D) with the base composition.
• the silicone pressure-sensitive adhesive layer can be obtained by coating the addition reaction-curable silicone pressure-sensitive adhesive composition for skin application of the present invention produced as described above on various substrates and curing it under predetermined conditions. .
• ⁇ Adhesive tape for attaching to skin For example, it can be suitably used as a pressure-sensitive adhesive tape for skin application having a substrate and an adhesive layer comprising a cured product of an addition-curable silicone pressure-sensitive adhesive composition for skin application on at least one surface of the substrate.
• a plastic film made of paper or plastic, a nonwoven fabric, a laminated film, glass, metal, cloth, and the like are selected.
• the paper include high quality paper, coated paper, art paper, glassine paper, polyethylene laminated paper, kraft paper, Japanese paper, and synthetic paper.
• plastic films polyethylene films, polypropylene films, polyester films, polyimide films, polyamide films, polyurethane films, polyurea films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, polycarbonate films, polytetrafluoroethylene films, Examples include a polystyrene film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a triacetyl cellulose film, a polyether ether ketone film, and a polyphenylene sulfide film.
• the nonwoven fabric include a synthetic fiber nonwoven fabric and a natural fiber nonwoven fabric.
• the laminate film examples include a laminate of a nonwoven fabric and a plastic film, a laminate of paper and a plastic film, and the like.
• the thickness and type of glass There is no particular limitation on the thickness and type of glass, and glass may be subjected to a chemical strengthening treatment or the like. Glass fiber can also be used, and the glass fiber may be used alone or in combination with another resin.
• the metal include an aluminum foil, a copper foil, a gold foil, a silver foil, and a nickel foil.
• a substrate that has been subjected to a primer treatment, a corona treatment, an etching treatment, or a plasma treatment may be used.
• the coating method may be a known coating method, such as a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, bar coater, kiss coater, gravure coater, screen coating. Coating, dip coating, cast coating and the like.
• the mixture may be appropriately diluted with the solvent described in the above optional component. In this case, a 20 to 60% by mass solution of the silicone pressure-sensitive adhesive composition can be obtained.
• the amount of coating is appropriately set according to the application, but usually, the amount is preferably such that the thickness of the cured silicone pressure-sensitive adhesive layer is 2 to 2,000 ⁇ m, particularly 3 to 1,000 ⁇ m.
• the curing condition of the addition reaction-curable silicone pressure-sensitive adhesive composition may be, but is not limited to, 70 to 250 ° C. for 10 seconds to 10 minutes.
• the pressure-sensitive adhesive tape for application to the skin of the present invention can also be produced by directly applying the addition reaction-curable silicone pressure-sensitive adhesive composition of the present invention to a substrate as described above, and curing it to form a silicone pressure-sensitive adhesive layer.
• the composition is applied to a release film or a release paper on which a release coating has been applied, and cured to form a silicone pressure-sensitive adhesive layer, and then the silicone pressure-sensitive adhesive layer is bonded to the above-described base material by a transfer method. May be.
• the pressure-sensitive adhesive tape for application to the skin of the present invention can be used by attaching it to the skin. Since the adhesive tape for applying to the skin has an appropriate adhesive strength to human skin, the base material can be firmly fixed to the skin, and the adhesive strength at the time of reapplying is small, so that reworkability and durability can be attained. It has excellent properties and can be used gently on human skin.
• the present invention will be described specifically with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.
• the viscosity is a value at 25 ° C.
• “part” indicates “part by mass”
• “characteristic value” indicates a value measured by the following test method.
• Me represents a methyl group
• Vi represents a vinyl group.
• A Component (A-1) Viscosity when dissolved in toluene to give a concentration of 30% by mass is 4,000 mPa ⁇ s, both ends of molecular chains are blocked with vinyl groups, and the following formula having a vinyl group content of 0.002 mol / 100 g is used.
• component (F) 0.2 part was added thereto, and n-heptane was added and mixed so that the solid content was about 60% by mass.
• An agent base composition A was synthesized.
• the component (A1) is (A-1) (8.0 parts), the component (A2) is (A-2) (72.0 parts), and the component (B) is (B-1) (20. 0 part), n-heptane (66.4 parts), and aqueous ammonia (0.5 part) were stirred at room temperature for 12 hours to obtain a condensation reaction product of components (A) and (B). . Next, this was heated at about 100 ° C. to 115 ° C. for 6 hours while refluxing to remove ammonia and water. After allowing the obtained reaction product to cool, component (F) (0.2 part) was added thereto, and n-heptane was added and mixed so that the solid content was about 60% by mass. An agent base composition G was synthesized.
• Examples 1 to 10 have moderate adhesive strength to human skin, have a small decrease in adhesive strength when re-applied, have excellent reworkability, It is clear that the silicone pressure-sensitive adhesive composition provides a pressure-sensitive adhesive layer exhibiting durability. On the other hand, it is apparent that Comparative Examples 1 to 6, which are out of the range of the present invention, cannot satisfy all of moderate adhesive strength, adhesive strength at the time of reattachment, reworkability, and durability. Therefore, the silicone pressure-sensitive adhesive composition of the present invention provides a pressure-sensitive adhesive layer exhibiting the above-described excellent performance, and the use value of a pressure-sensitive adhesive tape for skin application provided with this pressure-sensitive adhesive layer is high.
• the present invention is not limited to the above embodiment.
• the above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect.

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