Classifications

• • 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
  • C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • 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
  • 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
  • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

• the present invention relates to a novel addition-curable silicone elastomer composition able to exhibit appropriate hardness, physical strength and breaking elongation for a medical tube in particular.
• the present invention relates to a molded cured product of said silicone elastomer composition, and an elastic material for a medical device, and especially a medical tube, comprising the same.
• the present invention relates to an addition-curable silicone elastomer composition which can form a silicone elastomer having a cured product hardness, as measured in accordance with JIS K 6253 using a type A durometer hardness tester (hereinafter referred to as "JIS-A hardness” or “hardness”), of 40 or greater, having no surface tackiness, having a breaking elongation of 500% or greater and able to avoid the risk of breakage when formed into a tube due to exhibiting excellent tensile strength and tearing strength, and which is particularly useful for forming a medical catheter or a medical drain tube.
• JIS-A hardness type A durometer hardness tester
• Silicone elastomers exhibit excellent transparency, heat resistance, cold resistance, hardness, physical strength, durability and safety, and are therefore used in a wide variety of applications, including medical materials (for example, see Patent Documents 1 to 5).
• medical tubes are examples of elastic materials for medical devices that exhibit these properties.
• Medical tubes comprising silicone elastomers are physiologically inert and hardly react with body tissue when in contact with the human body, and are therefore used in catheters and drain tubes used in a variety of medical applications.
• medical tubes are inserted into body cavities such as the chest cavity and abdominal cavity, tracts such as the digestive tract and urinary tract, blood vessels and the like, and used to discharge body fluids or introduce a drip infusion such as a drug solution, nutritional supplement or imaging agent, and examples of such medical tubes include drainage tubes for aspirators used to remove discharges such as blood or pus following surgery and tubes for nutritional intake.
• An addition reaction-curable silicone elastomer composition does not generate by-products caused by degradation of organic peroxides, as is the case with organic peroxide curing type products, and can therefore be advantageously used as a silicone elastomer for this type of medical tube in the above-mentioned applications from the perspective of safety in particular.
• a publicly known addition reaction-curable silicone elastomer composition (for example, see Patent Document 6) exhibits insufficient tensile strength, tearing strength and breaking elongation at a hardness of 40 or greater, which is required for a medical tube.
• Patent Document 1 Japanese Unexamined Patent Application Publication No. S-55-040508
• Patent Document 2 Japanese Unexamined Patent Application Publication No. S-61 -255664
• Patent Document 3 Japanese Unexamined Patent Application Publication No. H-08-323857
• Patent Document 4 Japanese Unexamined Patent Application Publication No. 2011-162714A
• Patent Document 5 Japanese Unexamined Patent Application Publication No. 2012-012448A
• Patent Document 6 Japanese Unexamined Patent Application Publication No. 2007-217713A
• Patent Document 7 Japanese Unexamined Patent Application Publication No. H-07-331079
• An objective of the present invention is to provide a silicone elastomer composition able to form a silicone elastomer which has a JIS-A hardness of 40 or greater, which has excellent handlability with no surface tackiness, which can avoid the risk of breakage over a long period of time due to exhibiting high tearing strength and tensile strength, which does not break even when a material is stretched to an elongation of 500% or greater, and which does not have an elastic body yield point.
• an objective of the invention of the present application is to provide a molded cured product of said silicone elastomer composition, and an elastic material for a medical device obtained by using the same.
• an objective of the invention of the present application is to provide a medical tube, and especially a medical catheter or medical drain tube, which has excellent properties such as formability, safety, durability, and tensile strength, which are required for a medical tube, in which the above-mentioned hardness is 40 or greater, and which does not undergo permanent deformation even when an elastic load is applied.
• an addition-curable silicone elastomer composition that contains an organopolysiloxane which exhibits a raw rubber state at room temperature and contains silicon-bonded alkenyl groups, and is a mixture of organopolysiloxanes having a low content of silicon-bonded alkenyl groups and different alkenyl group bonding sites (component (A1 ), which has terminal alkenyl functional groups, and component (A2), which has terminal and side chain alkenyl functional groups) and (B) an organopolysiloxane having a high alkenyl group content, and contains an inorganic filler, and a molded cured product thereof, and thereby completed the present invention.
• component (A1 ) which has terminal alkenyl functional groups
• component (A2) which has terminal and side chain alkenyl functional groups
• B an organopolysiloxane having a high alkenyl group content, and contains an inorganic filler, and a molded cured product thereof, and
• (A1) an organopolysiloxane having: a number-average degree of polymerization of 2,000 or greater based on the number-average molecular weight in terms of polystyrene equivalent as measured by gel permeation chromatography (GPC), and an average of two or more silicon-bonded alkenyl groups at only the molecular terminals of the organopolysiloxane (A1 ),
• (A2) an organopolysiloxane having: a number-average degree of polymerization of 2,000 or greater based on the number-average molecular weight in terms of polystyrene equivalent as measured by gel permeation chromatography (GPC), an average of three or more alkenyl groups at the molecular terminals and in side chains, and an alkenyl group content of less than 0.10 wt.%;
• GPC gel permeation chromatography
• the silicone elastomer composition provides a cured product having: a hardness of 40 or greater, as measured in accordance with JIS K 6253 using a type A durometer hardness tester; and a breaking elongation of 500% or greater, as measured in accordance with JIS K 6251 , not having a maximum tensile stress value, which is a yield point of the cured product before breaking, on a tensile stress-elongation curve obtained in accordance with JIS K 6251 , and having a tensile strength of 7.0 MPa or greater, and thereby completed the present invention.
• component (B) is a mixture of alkenyl group-containing organopolysiloxanes which contains component (B1) and component (B2) below at a weight ratio of from 10/90 to 90/10, and thereby completed the present invention:
• (B1) an organopolysiloxane having: a number-average degree of polymerization of 2,000 or greater based on the number-average molecular weight in terms of polystyrene equivalent as measured by gel permeation chromatography (GPC), and an alkenyl group content of from 0.50 to 5.0 wt.%; and (B2) an organopolysiloxane having: a number-average degree of polymerization of 100 or less based on the number-average molecular weight in terms of polystyrene equivalent as measured by gel permeation chromatography (GPC), silanol groups at molecular terminals, and an alkenyl group content of from 1.00 to 20.0 wt.%.
• GPC gel permeation chromatography
• the inventors of the present invention found that it was possible to better solve the above-mentioned problems if the aforementioned inorganic filler of component (C) is an inorganic filler in which fumed silica having a BET specific surface area in the range of 150 to 350 m 2 /g accounts for 50 wt.% or greater of the total quantity of component (C), and thereby completed the present invention.
• the inventors of the present invention found that it was possible to solve the above-mentioned problems by means of a molded cured product of said silicone elastomer composition, and an elastic material for a medical device (and especially a medical tube) obtained by using the same, and thereby completed the present invention.
• a silicone elastomer composition able to form a silicone elastomer which has an appropriate hardness for a medical tube (a JIS-A hardness of 40 or greater), which has excellent handlability with no surface tackiness, which can avoid the risk of breakage over a long period of time due to exhibiting high tearing strength and tensile strength, which does not break even when a material is stretched to an elongation of up to 500% or greater, and which does not have an elastic body yield point.
• a medical tube a JIS-A hardness of 40 or greater
• FIG. 1 is a graph showing the tensile stress-elongation curve for Practical Example 1 shown in Table 1 (yield point: no).
• FIG. 2 is a graph showing the tensile stress-elongation curve for Practical Example 2 shown in Table 1 (yield point: no).
• FIG. 3 is a graph showing the tensile stress-elongation curve for Comparative Example 2 shown in Table 1 (yield point: yes).
• FIG. 4 is a graph showing the tensile stress-elongation curve for Practical Example 5 shown in Table 2 (yield point: no).
• FIG. 5 is a graph showing the tensile stress-elongation curve for Practical Example 6 shown in Table 2 (yield point: no).
• FIG. 6 is a graph showing the tensile stress-elongation curve for Comparative Example 3 shown in Table 2 (yield point: yes).
• FIG. 7 is a graph showing the tensile stress-elongation curve for Comparative Example 4 shown in Table 2 (yield point: yes).
• component (A) is the main component in the silicone elastomer composition according to the present invention, and is a characterizing component that realizes the physical properties of the composition.
• component (A) is an organopolysiloxane which exhibits a raw rubber state at room temperature, contains silicon-bonded alkenyl groups, has a low content of silicon-bonded alkenyl groups, and contains component (A1) and component (A2), which have ⁇ different alkenyl group bonding sites, at a weight ratio of from 10/95 to 95/5.
• Component (A) is an organopolysiloxane which has a number-average degree of polymerization of 2,000 or greater based on the number-average molecular weight in terms of standard polystyrene equivalent as measured by gel permeation chromatography (GPC)
• number-average degree of polymerization (hereinafter referred to as "number-average degree of polymerization"), and which exhibits a raw rubber state at room temperature, and which is represented by the average composition formula below, and contains component (A1) and component (A2), which have different alkenyl group bonding sites. Moreover, it is possible and preferable to remove low molecular weight siloxanes having degrees of polymerization of 10 or less from these components (A) to a content of 1 ,000 ppm or less in advance by using a publicly known means such as stripping.
• R may be the same or different and are substituted or unsubstituted monovalent hydrocarbon groups having from 1 to 10 carbons, and preferably from 1 to 8 carbons, and "a" is a positive number from 1.8 to 2.5, and preferably from 1.9 to 2.1.
• examples of the substituted or unsubstituted monovalent hydrocarbon groups bonded to silicon atoms represented by R above include alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups, cyclohexyl groups, octyl groups, nonyl groups and decyl groups; aryl groups such as phenyl groups, tolyl groups, xylyl groups and naphthyl groups; aralkyl groups such as benzyl groups, phenylethyl groups and phenylpropyl groups; alkenyl groups such as vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups and octen
• Component (A1) is an organopolysiloxane which has a number-average degree of polymerization of 2,000 or greater, has an average of two or more silicon-bonded alkenyl groups at only the molecular terminals of the component (A1), and exhibits a raw rubber state at room temperature.
• component (A1) is preferably a straight chain or partially branched organopolysiloxane in which the alkenyl group content is from 0.001 to 0.050 wt.%, and more preferably a straight chain organopolysiloxane having an average of two or more silicon-bonded alkenyl groups at both molecular terminals.
• the structure of component (A1) is such that the molecular terminals are capped by triorganosiloxy groups having silicon-bonded alkenyl groups and the main chain has a straight chain structure comprising repeating diorganosiloxane units, but may be a partially branched chain structure.
• the molecular weight of component (A1) is such that the number-average degree of polymerization is 2,000 or greater (from 2,000 to 100,000) and component (A1) exhibits in a raw rubber state, and the number-average degree of polymerization is preferably 3,000 or greater (from 3,000 to 8,000).
• the number-average degree of polymerization is less than the aforementioned lower limit, it is not possible to obtain a satisfactory rubbery feeling, the surface may become sticky or tacky and it is not possible to achieve the objective of the present invention even when used in combination with component (A2).
• Component (A2) is an organopolysiloxane which has a number-average degree of polymerization of 2,000 or greater, has an average of three or more alkenyl groups at molecular terminals and in side chains, has an alkenyl group content of less than 0.10 wt.%, and exhibits a raw rubber state at room temperature.
• Component (A2) has silicon-bonded alkenyl groups at molecular terminals and in side chains, but the alkenyl group content must be less than 0.10 wt.% and is preferably less than 0.095 wt.%, and more preferably from 0.001 to 0.090 wt.%. It is most preferable for the alkenyl group content in component (A2) to be from 0.010 to 0.080 wt.%.
• component (A2) is such that the molecular terminals are capped by triorganosiloxy groups having silicon-bonded alkenyl groups, the main chain has a straight chain structure comprising repeating diorganosiloxane units, and a part of the main chain contains one or more alkenyl group-containing diorganosiloxane units.
• component (A2) may be a straight chain organopolysiloxane in which one molecular terminal is capped by a triorganosiloxy group having silicon-bonded alkenyl groups and a part of the main chain contains two or more alkenyl group-containing diorganosiloxane units.
• component (A2) may be a partially branched chain structure.
• the molecular weight of component (A2) is such that the
• number-average degree of polymerization is 2,000 or greater (from 2,000 to 100,000) and component (A2) exhibits in a raw rubber state, and the number-average degree of polymerization is preferably 3,000 or greater (from 3,000 to 8,000). If the number-average degree of polymerization is less than the aforementioned lower limit, it is not possible to obtain a satisfactory rubbery feeling, the surface may become sticky or tacky and it is not possible to achieve the objective of the invention of the present application even when used in combination with component (A1).
• Component (A) in the present invention contains the above-mentioned components (A1) and (A2) at a weight ratio of from 10/90 to 95/5, and it is more preferable for the content of component (A1) to be higher than that of component (A2).
• a weight ratio of component (A1) / component (A2) is preferably from 30/70 to 90/10, more preferably from 50/50 to 85/15, and particularly preferably from 60/40 to 80/20. Meanwhile, if the proportion of component (A1) or component (A2) falls outside the aforementioned lower limit or upper limit, even if these
• components are used in combination, physical properties such as hardness and degree of elongation may deteriorate, the surface may become sticky or tacky and it is not possible to satisfactorily achieve the objective of the invention of the present application.
• these components may be mixed in advance when forming the composition, but may also be mixed separately with other components, and this preparation process has no adverse effect on the properties of the composition.
• Component (B) is component that imparts the silicone elastomer composition according to the present invention with the desired permanent elongation characteristics by being used in combination with component (A), and is characterized by having a more alkenyl group content than component (A).
• component (B) is an organopolysiloxane having an alkenyl group content of from 0.50 to 20.0 wt.%, and is a component that achieves these physical properties by being used in combination with component (A).
• component (B) is preferably an organopolysiloxane having an alkenyl group content of from 0.50 to 15.0 wt.%, and is more preferably two or more organopolysiloxanes having different degrees of polymerization.
• component (B) is preferably a mixture of alkenyl group-containing organopolysiloxanes which contains component (B1) and component (B2) at a weight ratio of from 5/95 to 90/10:
• (B1) an organopolysiloxane having: a number-average degree of polymerization of 2,000 or greater, and an alkenyl group content of from 0.50 to 5.0 wt.%;
• (B2) an organopolysiloxane having: a number-average degree of polymerization of 100 or less, silanol groups at molecular terminals, and an alkenyl group content of from 1.00 to 20.0 wt.%
• Component (B1) is an organopolysiloxane which has a number-average degree of polymerization of 2,000 or greater, and an alkenyl group content of from 0.50 to 5.0 wt.%, and exhibits a raw rubber state at room temperature.
• Component (B1) has silicon-bonded alkenyl groups at molecular terminals or in side chains, but preferably has alkenyl groups in side chains, and the silicon-bonded alkenyl group content is from 0.50 to 5.0 wt.%, preferably from 0.75 wt.% to less than 3.00 wt.%, and particularly preferably from 1.0 to 2.5 wt.%.
• component (B1) is such that the molecular terminals are capped with triorganosiloxy groups, the main chain has a straight chain structure comprising repeating diorganosiloxane units, and the organosiloxane units having alkenyl groups at some of the molecular terminals or side chains have an alkenyl group content of from 0.50 to 5.0 wt.%.
• component (B1) may be a partially branched chain structure.
• the molecular weight of component (B1) is such that the number-average degree of polymerization is 2,000 or greater (from 2,000 to 100,000) and component (B1) exhibits in a raw rubber state, and the number-average degree of polymerization is preferably 3,000 or greater (from 3,000 to 8,000). If the
• component (B1) being used in combination with component (A).
• component (B2) it is preferable for component (B2) to contain an organopolysiloxane which has a number-average degree of polymerization of 100 or less, silicon-bonded hydroxyl groups (silanol groups) at molecular terminals, and an alkenyl group content of from 1.00 to 20.0 wt.%.
• organopolysiloxane which has a number-average degree of polymerization of 100 or less, silicon-bonded hydroxyl groups (silanol groups) at molecular terminals, and an alkenyl group content of from 1.00 to 20.0 wt.%.
• Component (B2) has a lower degree of polymerization than the above-mentioned component (B1 ) and has silanol groups at both molecular terminals, and therefore has the advantage of being able to introduce a large number of crosslinkable groups into the composition without causing a cured product to become sticky or tacky or having an adverse effect on handlability and formability.
• This type of component (B2) is represented by the following structural formula.
• R 2 is a monovalent hydrocarbon group having from 1 to 6 carbons and not having an unsaturated aliphatic bond, and it is preferable for 90% or more of the R 2 groups to be methyl groups or phenyl groups.
• R 3 is an alkenyl group, preferably an alkenyl group having from 2 to 6 carbons, and more preferably a vinyl group or hexenyl group.
• the value of (n1+n2) is 0 to 98, and n1 and n2 are values whereby the alkenyl group content is from 1.00 to 20.0 wt.%.
• Component (B) of the present invention preferably contains the above-mentioned components (B1) and (B2) at a weight ratio of from 5/95 to 90/10, and it is more preferable for the content of component (B1) to be more than that of component (B2).
• a weight ratio of component (B1) / component (B2) is preferably from 5/95 to 50/50, more preferably from 5/95 to 40/60, and particularly preferably from 10/90 to 30/70.
• these components may be mixed in advance when forming the composition, but may also be mixed separately with other components, and this preparation process has no adverse effect on the properties of the composition.
• the content of component (B) is from 1.0 to 20 parts by weight, preferably from 1.5 to 15 parts by weight, and more preferably from 2.0 to 10 parts by weight, per 100 parts by weight of the component (A). If the usage quantity of component (B) is less than the aforementioned lower limit, the hardness of a cured product may be insufficient. Meanwhile, if the usage quantity of component (B) exceeds the aforementioned upper limit, elasticity decreases, the breaking elongation is less than 500%, and it may not be possible to achieve sufficient tensile strength, tearing strength and the like.
• the organopolysiloxane of component (C) is a crosslinking agent for the present composition, and is an organopolysiloxane having an average of two or more silicon-bonded hydrogen atoms in the molecule.
• the bonding sites of the silicon-bonded hydrogen atoms in component (B) are not particularly limited, and may be molecular terminals, side molecular chains or molecular terminals and side molecular chains.
• silicon-bonded groups other than hydrogen atoms in component (B) include monovalent hydrocarbon groups having no unsaturated aliphatic bonds, for example, alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups and hexyl groups; cycloalkyi groups such as cyclopentyl groups and cyclohexyl groups; aryl groups such as phenyl groups, tolyl groups and xylyl groups; aralkyl groups such as benzyl groups and phenethyl groups; halogenated alkyl groups such as
• component (C) is not limited, and may be, for example, straight chain, branched chain, straight chain having some branches, cyclic, dendritic (dendrimer-like) or resin-like.
• Component (C) may be a homopolymer having these molecular structures, a copolymer comprising these molecular structures or a mixture thereof.
• the viscosity of component (C) is not limited, but the viscosity at 25°C (as measured using a rotational viscometer and the like) is preferably from 1 to 100,000 mPa - s, more preferably from 1 to 10,000 mPa - s, and particularly preferably from 1 to 5,000 mPa - s.
• component (C) examples include methylhydrogenpolysiloxanes capped at both molecular terminals with trimethylsiloxy groups, copolymers of dimethylsiloxane and methyl hydrogen siloxane capped at both molecular terminals with trimethylsiloxy groups,
• dimethylpolysiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups methylhydrogenpolysiloxanes capped at both molecular terminals with dimethylhydrogensiloxy groups, copolymers of dimethylsiloxane and methyl hydrogen siloxane capped at both molecular terminals with dimethylhydrogensiloxy groups, cyclic methylhydrogenpolysiloxanes,
• organosiloxanes comprising siloxane units represented by the formula (Cr ⁇ SiO ⁇ , siloxane units represented by the formula (CH 3 ) 2 HSi0 1 /2 and siloxane units represented by the formula Si0 4 2 , tetra(dimethylhydrogensiloxy)silanes and methyltri(dimethylhydrogensiloxy)silanes.
• the content of component (C) is from 0.3 to 20 parts by weight per 100 parts by weight of component (A), and is preferably such that the amount of silicon-bonded hydrogen atoms in component (C) is from 1.0 to 20 moles, more preferably from 1.0 to 10 moles, and particularly preferably from 1.0 to 6 moles, per 1 mole of silicon-bonded alkenyl groups in component (A) and component (B).
• the content of component (C) is less than the lower limit of the above-mentioned range, crosslinking is inadequate, the hardness of the obtained cured silicone elastomer product is insufficient, the surface may become sticky or tacky and it is not possible to satisfactorily achieve the objective of the invention of the present application. Meanwhile, if the content of component (C) exceeds the upper limit of the
• a preferred compounded amount of component (C) is from 0.4 to 10 parts weight, and especially from 0.5 to 5 parts by weight, per 100 parts by weight of component (A).
• Component (D) is an inorganic filler, is essential in order to impart the silicone elastomer with satisfactory strength and is not particularly limited as long as the inorganic filler imparts the silicone elastomer with hardness and permanent elongation, as described below. It is possible to use one or more types of inorganic filler, and component (D) can be a reinforcing filler such as a silica fine powder or fumed titanium oxide; a non-reinforcing filler such as diatomaceous earth, an aluminosilicate, iron oxide, zinc oxide or calcium carbonate; or a thermally conductive filler such as aluminum oxide; fused silica or silver powder.
• a reinforcing filler such as a silica fine powder or fumed titanium oxide
• a non-reinforcing filler such as diatomaceous earth, an aluminosilicate, iron oxide, zinc oxide or calcium carbonate
• a thermally conductive filler such as aluminum oxide; fused si
• a silica fine powder can be a dry type silica such as fumed silica or a synthetic silica such as a wet type silica, and preferably has a specific surface area, as measured using the BET method, of 150 m 2 /g or greater, and more preferably from 250 to 350 m 2 /g.
• the surface of the silica fine powder may be treated with a silicon compound such as an organoalkoxysilane, an organohalosilane or an organosilazane, or a cyclic
• diorganosiloxane oligomer such as octamethyltetrasiloxane or decamethylpentasiloxane.
• the inorganic filler of component (D) is preferably an inorganic filler in which fumed silica having a BET specific surface area in the range of 150 to 350 m 2 /g accounts for 50 wt.% or greater of the total quantity of component (D), and particularly preferably an inorganic filler in which fumed silica having a BET specific surface area in the range of 150 to 350 m 2 /g accounts for 90 to 100 wt.% of the total quantity of component (D).
• the BET specific surface area of the fumed silica is preferably from 175 to 350 m 2 /g, and it is particularly preferable for the center value of the BET specific surface area to be from 200 to 325 m z /g.
• the inorganic filler of component (D) may be used without further modification, but is preferably treated in advance with a surface hydrophobization treatment agent or treated by adding a surface treatment agent when kneading with a silicone oil.
• These surface treatment agents may be one type of publicly known surface treatment agent, such as an alkylalkoxysilane, an alkylchlorosilane, an alkylsilazane, a silane coupling agent, a titanate-based treatment agent or a fatty acid ester, but it is also possible to use two or more of these surface treatment agents either simultaneously or at different times.
• the compounded amount of the inorganic filler of component (D) is preferably from 10 to 100 parts by weight, and especially from 25 to 75 parts by weight, per 100 parts by weight of component (A). It is not possible to achieve satisfactory hardness or physical strength if the compounded amount is less than the aforementioned lower limit, and elasticity deteriorates, tensile strength and breaking elongation in particular deteriorate, and the composition may not be suitable for use as a medical tube if the compounded amount exceeds the aforementioned upper limit.
• the addition reaction catalyst of component (E) is a catalyst used to facilitate curing of the present composition, and may be a platinum-based catalyst, a palladium-based catalyst, a rhodium-based catalyst and the like.
• a platinum metal-type catalyst is particularly preferred.
• component (E) examples include platinum-based catalysts, for example, platinum fine powders, platinum black, chloroplatinic acid, platinum tetrachloride, alcohol-modified chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, carbonyl complexes of platinum, powdered thermoplastic organic resins, such as methyl methacrylate resins, polycarbonate resins, polystyrene resins and silicone resins, containing these platinum-based catalysts; rhodium-based catalysts represented by the formulae [Rh(0 2 CCH 3 ) 2 ]2, Rh(0 2 CCH 3 ) 3 , Rh 2 (C 8 H 15 0 2 )4, Rh(C 5 H 7 0 2 ) 3 , Rh(C 5 H 7 0 2 )(CO) 2 , Rh(CO)[Ph 3 P](C 5 H 7 0 2 ), RhX 3 [(R) 2 S] 3 , (R 3
• X is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom
• Y is an alkyl group such as a methyl group or an ethyl group, CO, C 8 H 1 or 0.5C 8 H 12
• R is an alkyl group such as a methyl group, an ethyl group or a propyl group
• a cycloalkyl group such as a cycloheptyl group or a cyclohexyl group
• an aryl group such as a phenyl group or xylyl group
• R is an alkyl group such as a methyl group, an ethyl group or a propyl group
• an aryl group such as a phenyl group , a tolyl group or a xylyl group
• an alkoxy group such as a methoxy group or an ethoxy group
• the content of component (E) in the present composition is a catalytic quantity, but is more specifically an amount where the quantity of a platinum group metal in component (E) is from 0.01 to 1 ,000 ppm by weight, and preferably from 0.1 to 500 ppm by weight, relative to the total quantity of component (A) and component (B).
• the silicone elastomer composition according to the present invention must contain the above-mentioned components (A) to (E), but preferably also contains (F) a dimethylpolysiloxane which has silanol groups at molecular terminals and which has a number-average degree of polymerization of 100 or less.
• Component (F) does not have an addition reaction functional group (that is, a functional group which may take part in a hydrosilylation addition reaction and which comprises an alkenyl group such as a vinyl group and a silicon-bonded hydrogen atom (SiH group), is a dimethylpolysiloxane having a number-average degree of polymerization of 100 or less, and is represented by the average molecular formula below.
• R 2 is a monovalent hydrocarbon group having from 1 to 6 carbons and not having an unsaturated aliphatic bond, and it is preferable for 90% or more of the R 2 groups to be methyl groups or phenyl groups, n is a number in a range of 0 to 98.
• component (F) is an optional component that may be compounded if necessary, and the compounded amount thereof is from 0.1 to 50 parts by weight, and preferably from 1 to 20 parts by weight, per 100 parts by weight of component (A). If this compounded amount exceeds 50 parts by weight, there are concerns that the rubbery properties of a cured product will significantly deteriorate.
• the silicone elastomer composition according to the present invention contains from 5 to 100 parts by weight, and preferably from 10 to 75 parts by weight, of (G) an organopolysiloxane which has a number-average degree of polymerization of from 250 or more to a degree of polymerization whereby the composition exhibits a raw rubber state at room temperature based on the number-average molecular weight in terms of polystyrene equivalent as measured by gel permeation chromatography (GPC), is free of silicon-bonded alkenyl groups, and has at least one silanol group in the molecule.
• GPC gel permeation chromatography
• This component (G) is an organopolysiloxane which contains silanol groups and which has a fixed chain length, and therefore has the advantages of sufficiently suppressing an increase in hardness of an obtained cured product and being able to improve durability, tensile strength, tearing strength and the like when used in combination with the above-mentioned components (A) to (F).
• component (G) is such that component (G) is free of silicon-bonded alkenyl groups in the molecule, the molecular terminals are capped by silanol groups or triorganosiloxy groups, and the main chain has a straight chain structure comprising repeating diorganosiloxane units or repeating silanol organosiloxane units, but may be a partially branched chain structure.
• the degree of polymerization the number-average degree of polymerization may be from 250 or more to a degree of polymerization whereby the composition exhibits a raw rubber state at room temperature, and the number-average degree of polymerization is from 250 to 100,000, and preferably from 1 ,000 to 8,000.
• component (G) it is particularly preferable for component (G) to have a straight chain and to have a silanol group at both molecular terminals, and in such cases, component (G) is represented by the average molecular formula below. Moreover, it is possible and preferable to remove low molecular weight siloxanes having degrees of polymerization of 10 or less from component (G) to a content of 1 ,000 ppm or less in advance by using a publicly known means such as stripping.
• R 2 is a monovalent hydrocarbon group having from 1 to 6 carbons and not having an unsaturated aliphatic bond, and it is preferable for 90% or more of the R 2 groups to be methyl groups or phenyl groups.
• the value of ml + m2 is 248 or more, ml is a positive number, and m2 is 0 or a positive number.
• component (G) is particularly preferable for component (G) to be an organopolysiloxane which has a number-average degree of polymerization of 2,000 or greater based on the number-average molecular weight in terms of standard polystyrene equivalent, exhibits a raw rubber state at room temperature, is free of silicon-bonded alkenyl groups in the molecule, and has a silanol group at both molecular terminals.
• organopolysiloxane which has silanol terminals and which exhibits a raw rubber state, it is possible to further improve permanent elongation
• magnesium oxide MgO
• magnesium hydroxide Mg(OH) 2
• magnesium carbonate salts examples include magnesium carbonate (MgC0 3 ) and basic magnesium carbonates
• magnesium compounds may be hydrates or anhydrates.
• two or more magnesium compounds may be used in combination. Because such magnesium compounds have been approved for use by the FDA, the silicone elastomer composition of the present invention may be advantageously used in food/drink applications in addition to medical applications.
• silicone elastomers that contain these magnesium compounds are in contact for long periods of time with aqueous media that contain chloride ions (including balloon-enlarging solutions that are non-toxic to humans, such as tap water, physiological saline, mixtures of angiographic agents and physiological saline, glucose solutions, bodily fluids such as blood and gastric acid, and drug solutions for treatment), it is possible to prevent or reduce degradation or the occurrence of appearance defects such as whitening, and the silicone elastomer composition of the present invention can be advantageously used in medical components that come into contact with blood, gastric acid, physiological saline, acidic cleaning solutions and the like (for example, stomach catheters, balloons, catheter balloons, artificial dialysis machines, blood dialysis machines and implant components).
• aqueous media that contain chloride ions including balloon-enlarging solutions that are non-toxic to humans, such as tap water, physiological saline, mixtures of angiographic agents and physiological saline, glucose solutions, bodily fluids such as
• the lower limit of the compounded amount of the aforementioned magnesium compounds is not particularly limited as long as the above-mentioned effect can be achieved, but this
• compounded amount is preferably from 0.01 to 3 wt.%, and more preferably from 0.1 to 0.5 wt.%, relative to the total weight (mass) of the curability silicone elastomer composition.
• the form of the aforementioned magnesium compounds is not particularly limited, and can be, for example, bulk-like or particulate (including a regular spherical shape or an approximately spherical shape), but is preferably particulate.
• the average particle diameter of a particulate magnesium compound is generally from 0.1 to 10 ⁇ , and particularly preferably from 0.5 to 5 pm.
• a surface treatment agent such as an aluminum compound, a zinc compound, a silicon compound or a higher fatty acid.
• the addition-curable silicone elastomer composition according to the present invention may contain a curing retarder in order to adjust the curing speed or pot life.
• curing retarders include alcohol derivatives having carbon-carbon triple bonds, such as
• the compounded amount of the curing retarder may be selected as appropriate according to the usage method, molding method and the like of the addition-curable silicone elastomer composition.
• a commonly used compounded amount is from 0.001 to 5 wt.% (mass%) relative to the total weight (mass) of the composition.
• the addition-curable silicone elastomer composition according to the present invention may contain carbon black such as acetylene black, furnace black or channel black as long as the objective of the present invention is not impaired.
• the addition-curable silicone elastomer composition according to the present invention may, if necessary, contain additives such as pigments (coloring agents such as red iron oxide and organic pigments, titanium dioxide and the like), heat-resistant agents, flame retardants, internal release agents, plasticizers, non-functional silicone oils and the like).
• examples of internal release agents include higher fatty acid salts such as calcium stearate.
• additives such as heat-resistant agents and flame retardants when the addition-curable silicone elastomer composition according to the present invention is used as a medical tube in an environment that is exposed to high temperatures, such as in heat sterilization or in a thermocouple.
• the addition-curable silicone elastomer composition according to the present invention to contain essentially no (X1 ) an organopolysiloxane capped at both molecular terminals with trialkylsilyl groups (excluding compounds corresponding to the component (B) of the component (C)) or (X2) an organopolysiloxane resin essentially comprising R 1 3 Si0 1/2 units (wherein R 1 are each independently hydroxyl groups, alkoxy groups having from 1 to 6 carbons or substituted or unsubstituted monovalent hydrocarbon groups having from 1 to 10 carbons) and Si0 4 /2 units.
• the total content of these components is preferably less than 5 wt.% of the overall composition, more preferably less than 1 wt.%, and most preferably a quantity that has essentially no effect on the properties of the cured product, that is, not contained in the composition (less than 0.1 wt.%).
• the addition-curable silicone elastomer composition according to the present invention contains a substantial quantity of the above-mentioned organopolysiloxane capped at both molecular terminals with trialkylsilyl groups of component (X1) or the organopolysiloxane resin of component (X2), stickiness and tackiness occur in a cured product, meaning that handlability deteriorates and such a composition may not be suitable for use as an elastic material for a medical device such as a medical tube.
• the content of the organopolysiloxane capped at both molecular terminals with trialkylsilyl groups of component (X1) exceeds 5 wt.% of the overall composition, stickiness and tackiness occurs in a cured product, and even if the composition is useful in terms of hardness or permanent elongation characteristics, there may be an adverse effect on handlability (such as roll applicability) or formability (such as mold release properties).
• the curable silicone rubber composition of the present invention can be easily produced by homogeneously mixing a composition that contains the above-mentioned components and, if necessary, a variety of additives using a publicly known kneading means such as a Ross mixer, a two roll mill or a kneader mixer.
• a publicly known kneading means such as a Ross mixer, a two roll mill or a kneader mixer.
• the method for molding or curing the addition-curable silicone elastomer composition according to the present invention may be a commonly used method, but the molding method is preferably an injection molding method, a compression molding method or an extrusion molding method (including hot air vulcanization).
• curing conditions such as the curing temperature and the curing time are not particularly limited, and good curing is generally carried out at a temperature from room temperature to 220°C. From the perspective of industrial production of an elastic material for a medical device such as a medical tube, it is possible to use heat curing conditions of from 80 to 230°C for a period of from 3 seconds to 60 minutes, and preferably from 100 to 200°C for a period of from 5 seconds to 30 minutes.
• by press curing is preferably an injection molding method, a compression molding method or an extrusion molding method (including hot air vulcanization).
• curing conditions such as the curing temperature and the curing time are not particularly limited, and good curing is generally carried out at a temperature from room temperature to 220°
• an elastic material for a medical device can exhibit appropriate hardness and permanent elongation characteristics, but it is also possible to cure the composition by means of a stepwise vulcanization (step curing) process, such as carrying out primary vulcanization and then carrying out secondary vulcanization. In such cases, however, the cycle time required for production may be increased and productivity may decrease.
• step curing step curing
• the addition-curable silicone elastomer composition according to the present invention may be cured in a single step at the above-mentioned temperatures. Furthermore, characteristics such as permanent elongation may be further improved by step curing in which the composition is first heated to a temperature from room temperature to 150°C, and preferably from 60 to 150°C, and then heated to from 80 to 200°C, and preferably from 100 to 180°C. In addition, in order to remove small quantities or trace quantities of volatile components and further improve characteristics such as permanent elongation, it is preferable to carry out secondary vulcanization (heat aging) at from 150 to 250°C for a period of from 10 minutes to 2 hours following completion of the curing.
• secondary vulcanization heat aging
• the addition-curable silicone elastomer composition according to the present invention is characterized by providing a cured product having a hardness, as measured in accordance with JIS K 6253 using a type A durometer hardness tester (JIS-A hardness), of 40 or greater following press curing at 120°C for 10 minutes.
• the JIS-A hardness is preferably from 40 to 90, and more preferably from 45 to 85.
• the JIS-A hardness is preferably 50 or greater, and more preferably from 50 to 80. If the hardness falls outside the aforementioned range when using the above-mentioned curing conditions, the strength and flexibility of the cured product may be insufficient and the cured product may not be suitable for use as a medical balloon.
• the addition-curable silicone elastomer composition according to the present invention is characterized by having a breaking elongation, as measured in accordance with JIS K 6251 , of 500% or greater, and not having a yield point of a cured product before breaking following press curing at 120°C for 10 minutes.
• a cured product having a yield point means that on a tensile stress-elongation curve obtained in accordance with JIS K 6251 , a maximum tensile stress value of the cured product is present from the initial tensile stress being applied to the cured product breaking.
• the addition-curable silicone elastomer composition according to the present invention is such that a maximum tensile stress value of the cured product is not observed from the initial tensile stress being applied to the cured product breaking when plotting a tensile stress-elongation curve (SS curve) obtained in accordance with JIS K 6251 due to the tensile stress and elongation both increasing without reaching a maximum value up to the point at which the above-mentioned breaking elongation is measured (that is, up to the point of breaking), and when further stretched, the sample breaks at a breaking elongation of 500% or greater.
• SS curve tensile stress-elongation curve
• the cured product of the addition-curable silicone elastomer composition according to the present invention has a tensile strength, as specified in JIS K 6251 , of 7.0 MPa or greater, more preferably from 8.0 to 15 MPa, and particularly preferably from 8.25 to 14.0 MPa.
• the cured product has a breaking elongation, as specified in JIS K 6251 , of 500% or greater, and preferably from 500 to 1 ,200%.
• the breaking elongation is preferably from 500 to 900% when the aforementioned hardness is from 60 to 80, and more preferably from 800 to 1 ,200% when the aforementioned hardness is from 40 to 60.
• Physical properties such as the above-mentioned hardness, breaking elongation, tensile strength and lack of yield point (maximum tensile stress value on a tensile stress-elongation curve obtained in accordance with JIS K 6251) are physical properties that are achieved as a direct result of the constitution of the addition-curable silicone elastomer composition according to the present invention, and especially as a result of using the prescribed components (A) and (B).
• the addition-curable silicone elastomer composition according to the present invention has a 100% modulus (M100), as measured in accordance with JIS K 6251 , of from 0.75 to 5.0 MPa, and particularly preferably from 1.0 to 3.0 MPa, following press curing at 120°C for 10 minutes.
• M100 modulus
• the addition-curable silicone elastomer composition according to the present invention preferably has a tearing strength, as measured in accordance with JIS K 6252 using a crescent mold, of 20 kN/m or more, and especially from 25.0 to 50 kN/m.
• a cured product comprising the silicone elastomer composition according to the present invention can be used in a variety of applications, such as electrical equipment, vehicles, construction, medical care and foods.
• a cured product comprising the silicone elastomer composition according to the present invention can be used in rubber contacts for remote controllers, typewriters, word processors, computer terminals, musical instruments and the like; gaskets for construction; rollers such as copier rollers, developing rollers, transfer rollers, charging rollers and paper feed rollers; rubber vibration insulators for motorcycles and the like; packing for compact disks used in computers and the like; water distribution components such as valves, hoses, tubes, packing, seals and joints; children's toys, tableware, cookware (including silicone steamers), toothbrushes, teats for baby bottles, infants' pacifiers, artificial teats, sporting goods, underwater eyeglasses for diving, goggles for diving, vehicle components, scale models and artificial skin components for robots.
• a cured product comprising the silicone elastomer composition according to the present invention exhibits excellent safety and durability and exhibits appropriate hardness, permanent elongation and other physical properties, and can therefore be used in elastic medical materials used to treat humans or animals.
• a cured product comprising the silicone elastomer composition according to the present invention is also suitable for use in a variety of medical tubes, stomach catheters, medical balloons, catheter balloons, artificial dialysis machines, blood dialysis machines, implant components, chemical stoppers and O-rings.
• a cured product comprising the silicone elastomer composition according to the present invention exhibits excellent heat resistance, acid resistance, radiation resistance and the like and does not suffer from a deterioration in physical properties, and can therefore be easily sterilized.
• the most suitable application for the silicone elastomer according to the present invention is as a material for medical devices, such as a variety of medical catheters and tubes, and the silicone elastomer according to the present invention can be used most advantageously as a material for a variety of medical tubes that are inserted into body cavities such as the chest cavity and abdominal cavity, tracts such as the digestive tract and urinary tract, blood vessels and the like, and used to discharge body fluids or introduce a drip infusion such as a drug solution, nutritional supplement or imaging agent.
• a medical tube comprising the silicone elastomer according to the present invention achieves the advantages of excellent formability for extrusion molding and the like, relatively high hardness, high breaking elongation, excellent flexibility and lack of permanent deformation.
• the silicone elastomer according to the present invention has high tensile strength and tearing strength and excellent reliability and durability.
• fumed silica as the aforementioned preferred inorganic filler, it is possible to obtain a silicone elastomer having a transparent appearance, excellent scratch resistance, and excellent visibility of the contents of a tube or the flow of a liquid in a catheter.
• the silicone elastomer according to the present invention can be easily molded, and the shape, internal structure, internal diameter, film thickness, length and the like of the tube can be selected as appropriate according to the intended use of the tube or the organ in which the tube is to be used.
• a medical tube comprising the silicone elastomer according to the present invention is a medical catheter or medical drain tube, examples of which include medical catheters for drip infusions of blood and the like, drainage tubes for aspirators used to remove discharges such as blood or pus following surgery, tubes for nutritional intake following surgery such as percutaneous endoscopic gastrostomy (PEG), and tubes for pharmaceuticals/preparations.
• medical catheters for drip infusions of blood and the like drainage tubes for aspirators used to remove discharges such as blood or pus following surgery
• tubes for nutritional intake following surgery such as percutaneous endoscopic gastrostomy (PEG), and tubes for pharmaceuticals/preparations.
• PEG percutaneous endoscopic gastrostomy
• organopolysiloxane is the number-average degree of polymerization, based on the
• Comparative Examples 1 to 4 Moreover, Table 1 shows Practical Examples and Comparative Examples relating to silicone elastomers prepared so as to have hardnesses of 60 or greater, and Table 2 shows Practical Examples and Comparative Examples relating to silicone elastomers prepared so as to have hardnesses of from 40 to less than 60.
• JIS-A hardness The hardness of a cured silicone rubber sample was measured in accordance with JIS K 6251 (tensile testing methods for vulcanized rubber) (JIS-A hardness, measured using a JIS type A durometer).
• the tearing strength was measured in accordance with JIS K 6252 using an "Autograph SES-1000" manufactured by Shimadzu Corporation.
• Fumed silica having a BET specific surface area of 300 m2/g (product name "Aerosil 300", manufactured by Nippon Aerosil)
• Fumed silica having a BET specific surface area of 200 m2/g (product name "Aerosil 200", manufactured by Nippon Aerosil)
• each of the compositions of Practical Examples 1 to 6 was press cured at 120°C for 10 minutes to provide a silicone elastomer which had an appropriate hardness for an elastic medical material (especially a medical tube), had no yield point, had a high breaking elongation and had high tensile strength.
• Comparative Example 1 had no yield point, but had insufficient breaking elongation and tearing strength.
• Comparative examples 2 to 5 each had a yield point, which is a maximum tensile stress value from the initial tensile stress being applied to the cured product breaking when plotting a tensile stress-elongation curve (SS curve) obtained in accordance with JIS K 6251 , and could not therefore provide a silicone elastomer having the characteristic of exhibiting no yield point.
• SS curve tensile stress-elongation curve

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