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
  • C08L83/04—Polysiloxanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
  • A61L29/04—Macromolecular materials
  • A61L29/049—Mixtures of macromolecular compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
  • A61L29/04—Macromolecular materials
  • A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
  • A61L29/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
  • A61L29/126—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3081—Treatment with organo-silicon compounds
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/006—Additives being defined by their surface area
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/02—Applications for biomedical use

Definitions

• the present invention relates to a silicone rubber-based hardening resin composition, a molded article using the silicone rubber-based hardening resin composition, and a medical tube using the molded article.
• silicone rubber Since silicone rubber is excellent in heat resistance, flame resistance, chemical stability, weather resistance, radiation resistance, electrical properties, and the like, it has been used for a variety of uses in a wide range of areas. In particular, since silicone rubber is physiologically inactive and reacts little with body tissues when the silicone rubber is in touch with a living body, it has been used as a material for medical instruments such as medical catheters.
• the medical catheter is a tube which is inserted into a body cavity such as a thoracic cavity and an abdominal cavity, a lumen such as an alimentary canal and a ureter, and a blood vessel, and used to discharge a body fluid, or injecting or dripping a drug solution, nutrition, or a contrast medium.
• the medical catheter is required to have scratch resistance (tear resistance), kink resistance (tensile strength), transparency, flexibility (tensile elongation properties), and the like, in addition to biocompatibility.
• the medical catheter is used as a drainage tube of an aspirator for removing an effluent such as blood, and pus after a surgery operation, and a tube for intaking nutrient after a surgical operation such as percutaneous endoscopic gastrostomy (PEG).
• an effluent such as blood, and pus after a surgery operation
• a tube for intaking nutrient after a surgical operation such as percutaneous endoscopic gastrostomy (PEG).
• PEG percutaneous endoscopic gastrostomy
• the silicone rubber composition which is a raw material of the silicone rubber, is required to have extrusion molding properties.
• soft polyvinyl chloride is also widely used in addition to silicone rubber.
• silicone rubber is excellent in biocompatibility and flexibility, but required to have improved strength such as tear resistance, and tensile strength, in particular, tear resistance.
• tear resistance When the tear resistance is insufficient, the catheter may be torn by the damage made by a needle or a blade used during a surgical operation.
• tensile strength When the tensile strength is insufficient, the catheter may be bent and closed (kinked), and thereby, a flow of a body fluid which should be discharged or a drug solution which should be injected may be stagnated.
• Patent Documents Nos. 1 to 8 In order to improve the tear strength and tensile strength of silicone rubber, various methods have been suggested (for example, Patent Documents Nos. 1 to 8).
• Patent Document No. 1 discloses a hardening silicone rubber composition which contains mainly organopolysiloxane having high viscosity and containing a small amount of a vinyl group (crude rubber (A)), and is added with organopolysiloxane having low viscosity and containing a large amount of a vinyl group (silicone oil (B)), an organopolysiloxane copolymer containing a vinyl group (silicone resin containing a vinyl group (C)), organo-hydrogen siloxane (crosslinking agent (D)), platinum or a platinum compound (hardening catalyst (E)), and fine powdered silica (filler (F)).
• a hardening silicone rubber composition which contains mainly organopolysiloxane having high viscosity and containing a small amount of a vinyl group (crude rubber (A)), and is added with organopolysiloxane having low viscosity and containing a large amount of
• Patent Document No. 1 Japanese Unexamined Patent Application, First Publication No. Hei 7-331079
• Patent Document No. 2 Japanese Unexamined Patent Application, First Publication No. Hei 7-228782
• Patent Document No. 3 Japanese Unexamined Patent Application, First Publication No. Hei 7-258551
• Patent Document No. 4 U.S. Pat. No. 3,884,866
• Patent Document No. 5 U.S. Pat. No. 4,539,357
• Patent Document No. 6 U.S. Pat. No. 4,061,609
• Patent Document No. 7 U.S. Pat. No. 3,671,480
• Patent Document No. 8 Japanese Unexamined Patent Application, First Publication No. 2005-68273
• Examples of a method for applying high tear resistance to silicone rubber include addition of an inorganic filler such as silica fine particles, and changing the crosslinking density (distributing an area at which the crosslinking density is high and an area at which the crosslinking density is low in the silicone rubber).
• an inorganic filler such as silica fine particles
• changing the crosslinking density distributing an area at which the crosslinking density is high and an area at which the crosslinking density is low in the silicone rubber.
• the mechanical strength, in particular, the tear strength of the silicone rubber is desired to be further improved.
• the silicone rubber is desired to have a certain level of hardness.
• a target part for example, thoracic cavity
• the catheter is easily deformed due to insertion resistance, this means “no elasticity”, and easily closed due to low kink resistance.
• the mechanical strength of the silicone rubber is desired to be improved.
• the silicone rubber excellent in tear strength and hardness is desired to be developed.
• an object of the present invention is to provide a silicone rubber-based hardening composition which can produce a silicone rubber having excellent tear strength.
• Another object of the present invention is to provide a silicone rubber-based hardening composition which can produce a silicone rubber having excellent tensile strength, tear strength, and hardness.
• a silicone rubber-based hardening composition containing:
• m denotes an integer from 0 to 300; n denotes an integer represented by (300 ⁇ m); R 4 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group; R 5 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group; at least two of plural R 4 and R 5 are a hydride group; and R 6 denotes an alkyl group, aryl group, which contains 1 to 8 carbon atoms, and has a substituted group or no substituted group, or a hydrocarbon group in which these groups are combined.
• silicone rubber-based hardening composition according to any one of (1) to (3), wherein the silane coupling agent having a trimethylsilyl group is at least one selected from the group consisting of silazane, chlorosilane, and alkoxysilane.
• silicone rubber-based hardening composition according to any one of (1) to (4), wherein the silane coupling agent having a trimethylsilyl group is at least one selected from the group consisting of hexamethyldisilazane, trimethylchlorosilane, trimethylmethoxysilane, and trimethylethoxysilane.
• silicone rubber-based hardening composition according to any one of (1) to (10), wherein the silicone rubber-based hardening composition contains 0.1 parts by weight to 5 parts by weight of the linear organohydrogen polysiloxane (B), and 20 parts by weight to 150 parts by weight of the silica filler (C) of which the surface is treated with a silane coupling agent having a trimethylsilyl group, relative to 100 parts by weight of the linear organopolysiloxane having a vinyl group (A).
• silicone rubber-based hardening composition according to any one of (1) to (11), wherein the silicone rubber-based hardening composition further contains a catalyst quantity of platinum or a platinum compound.
• a silicone rubber-based hardening composition containing:
• m denotes an integer from 0 to 300; n denotes an integer represented by (300 ⁇ m); R 4 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group; R 5 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group; at least two of plural R 4 and R 5 are a hydride group; and R 6 denotes an alkyl group, aryl group, which contains 1 to 8 carbon atoms, and has a substituted group or no substituted group, or a hydrocarbon group in which these groups are combined.
• silane coupling agent having an organosilyl group containing a vinyl group is at least one selected from the group consisting of methacryloxypropyl triethoxysilane, methacryloxypropyl trimethoxysilane, methacryloxypropyl methyldiethoxysilane, methacryloxypropyl methyldimethoxysilane, divinyl tetramethyldisilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinylmethyldimethoxysilane.
• the silicone rubber-based hardening composition according to any one of (15) to (24), wherein the linear organopolysiloxane having a vinyl group (A) contains a first linear organopolysiloxane having a vinyl group (A1) containing 0.05% by mole to 0.2% by mole of a vinyl group, and a second linear organopolysiloxane having a vinyl group (A2) containing 0.5% by mole to 12% by mole of a vinyl group.
• silicone rubber-based hardening composition according to any one of (15) to (27), wherein the silicone rubber-based hardening composition contains 0.1 parts by weight to 5 parts by weight of the linear organohydrogen polysiloxane (B), 20 parts by weight to 150 parts by weight of the silica filler (C) of which the surface is treated with a silane coupling agent having a trimethylsilyl group, and 0.5 parts by weight to 100 parts by weight of the silica filler (D) of which the surface is treated with a silane coupling agent having an organosilyl group containing a vinyl group, relative to 100 parts by weight of the linear organopolysiloxane having a vinyl group (A).
• the silicone rubber-based hardening composition contains 0.1 parts by weight to 5 parts by weight of the linear organohydrogen polysiloxane (B), 20 parts by weight to 150 parts by weight of the silica filler (C) of which the surface is treated with a silane coupling agent having a trimethylsily
• the silicone rubber obtained by hardening the silicone rubber-based hardening composition according to the present invention is excellent in mechanical strength such as tensile strength and tear strength, in particular, tear strength. Therefore, the molded article which is obtained by using the silicone rubber-based hardening composition and the medical tube which is obtained by using the molded article have high mechanical strength. In other words, according to the present invention, it is possible to produce a medical catheter made of silicone rubber which is excellent in scratch resistance and kink resistance, in particular, scratch resistance.
• the silicone rubber which is obtained by hardening the silicone rubber-based hardening composition according to the present invention, is excellent in balance between mechanical strength, in particular, tensile strength, tear strength, and hardness. Therefore, the molded articles made of the silicone rubber-based hardening composition, and the medical tube made of the molded article have high mechanical strength, such as tensile strength, tear strength, and hardness. In other words, according to the present invention, it is possible to produce a medical catheter made of silicone rubber which is excellent in kink resistance, scratch resistance, and ease of insertion.
• the silicone rubber-based hardening composition according to the present invention contains linear organopolysiloxane having a vinyl group (A), linear organohydrogen polysiloxane (B), and silica filler (C) of which the surface is treated with a silane coupling agent having a trimethylsilyl group.
• silica filler is often added in the silicone-based hardening composition.
• the tear strength could be remarkably improved by adding silica filler of which the surface is treated with a specific silica coupling agent in silicone rubber containing a specific matrix containing the linear organopolysiloxane having a vinyl group (A), and the linear organohydrogen polysiloxane (B) as raw material.
• the present inventors found that the mechanical strength, in particular, tear strength, of silicone rubber could be improved by combining the linear organopolysiloxane having a vinyl group (A), the linear organohydrogen polysiloxane (B), and the silica filler (C) of which the surface is treated with a silane coupling agent having a trimethylsilyl group in advance (this may be simply denoted by “trimethylsilyl group-surface treated silica filler (C)” below).
• the tear strength of the silicone rubber could be remarkably improved while maintaining the tensile strength by combining the linear organopolysiloxane having a vinyl group (A), the linear organohydrogen polysiloxane (B), and the silica filler (C) of which the surface is previously treated with a silane coupling agent having a trimethylsilyl group, compared with a combination between the linear organopolysiloxane having a vinyl group (A), the linear organohydrogen polysiloxane (B), and the silica filler of which the surface is treated with a silane coupling agent having a methylsilyl group (dimethyl dichlorosilane).
• silica filler as filler which is combined between the linear organopolysiloxane having a vinyl group (A), and the linear organohydrogen polysiloxane (B), and treating the surface of the silica filler with a silane coupling agent having a trimethylsilyl group in advance can be presumed as shown below.
• the hydrophobic property of the silica filler is increased by treating the surface of the silica filler with the silane coupling agent having a trimethylsilyl group, and the cohesive force of the silica filler in the silicone rubber-based hardening composition containing the linear organopolysiloxane having a vinyl group (A), the linear organohydrogen polysiloxane (B) is decreased (condensation due to the hydrogen bond by the silanol group is decreased), and thereby, the dispersibility of the silica filler in the composition is improved.
• the interface between the silica filler and the rubber matrix is increased by the improvement of the dispersibility of the silica filler, and the number of the rubber molecular chains, which are affected by the silica filler, are increased.
• the molecular mobility of the rubber molecular chains, which are affected by the silica filler is decreased by the interaction with the silica filler.
• the rubber molecular chain is hard compared with an area having high molecular mobility.
• the tear behavior in silicone rubber when an initial crack grows and spreads, and tear stress is applied to the hard area, the hard area resists the tear stress. As a result, the tear strength is increased.
• the silane coupling agent having a dimethylsilyl group has been known as a surface treatment agent for making an inorganic filler hydrophobic.
• the silicone rubber obtained by using the silane coupling agent having a dimethylsilyl group has remarkably lower tear strength compared with the silicone rubber obtained by using the silane coupling agent having a trimethylsilyl group.
• the reason for causing the large difference in the tear strength can be presumed to be because the silane coupling agent having a dimethylsilyl group has lower cohesive-decrease effects compared with the silane coupling agent having a trimethylsilyl group.
• the silicone rubber which is obtained by hardening the silicone rubber-based hardening composition according to the present invention has excellent tensile strength and tear strength. Therefore, it is possible to obtain the catheter made of the silicone rubber which is excellent in scratch resistance and kink resistance by using the silicone rubber-based hardening composition according to the present invention.
• the silicone rubber-based hardening composition according to the present invention essentially contains the following components (A) to (C).
• the linear organopolysiloxane having a vinyl group is a main component in the silicone rubber-based hardening composition according to the present invention, and this is a polymer having a linear structure.
• This linear organopolysiloxane has a vinyl group, and the vinyl group becomes a crosslinking point when vulcanization is carried out.
• the amount of the vinyl group in the linear organopolysiloxane having a vinyl group is not particularly limited. However, the amount of the vinyl group is preferably in a range of 0.01 to 15% by mole, and more preferably in a range of 0.05 to 12% by mole.
• the amount of the vinyl group in the linear organopolysiloxane having a vinyl group means the molar percentage of the siloxane unit having a vinyl group when the total unit of the linear organopolysiloxane having a vinyl group (A) is assumed to 100% by mole. At this time, one siloxane unit having a vinyl group is regarded to have one vinyl group.
• the polymerization degree of the linear organopolysiloxane having a vinyl group (A) is not particularly limited. However, the polymerization degree is generally in a range of 3,000 to 10,000, and preferably in a range of 4,000 to 8,000.
• the specific gravity of the linear organopolysiloxane having a vinyl group (A) is generally in a range of 0.9 to 1.1.
• the linear organopolysiloxane having a vinyl group (A) preferably has a structure represented by the formula (1) below.
• R 1 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, or a hydrocarbon group in which these groups are combined.
• alkyl group which contains 1 to 10 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these alkyl groups, a methyl group is preferable.
• Examples of the alkenyl group which contains 1 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Among these alkenyl groups, a vinyl group is preferable.
• the aryl group which contains 1 to 10 carbon atoms include a phenyl group.
• R 2 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, or a hydrocarbon group in which these groups are combined.
• alkyl group which contains 1 to 10 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these alkyl groups, a methyl group is preferable.
• Examples of the alkenyl group which contains 1 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group.
• Examples of the aryl group which contains 1 to 10 carbon atoms include a phenyl group.
• R 3 denotes an alkyl group, aryl group, which contains 1 to 8 carbon atoms, and has a substituted group or no substituted group, or a hydrocarbon group in which these groups are combined.
• alkyl group which contains 1 to 8 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these alkyl groups, a methyl group is preferable.
• aryl group which contains 1 to 8 carbon atoms include a phenyl group.
• Examples of the substituted group in R 1 and R 2 which have a substituted group in the formula (1) include a methyl group, and a vinyl group.
• Examples of the substituted group in R 3 which has a substituted group in the formula (1) include a methyl group.
• plural R 1 are independent to each other, and may be the same or not.
• plural R 2 and R 3 are independent to each other, and may be the same or not, similar to R 1 .
• At least one of plural R 1 and R 2 has a vinyl group. That is, at least one of plural R 1 and R 2 is an alkenyl group.
• m and n are the number of repeating units that constitute the linear organopolysiloxane having a vinyl group (A) represented by the formula (1), m is an integer from 1 to 1,000, and n is an integer from 3,000 to 10,000. m is preferably in a range of 40 to 700, and n is preferably in a range of 3,600 to 8,000.
• a specific structure of the linear organopolysiloxane having a vinyl group (A) represented by the formula (1) includes the following structure represented by the formula (1-1) below.
• R 1 and R 2 are independently a methyl group or a vinyl group, and at least one of R 1 and R 2 is a vinyl group.
• the linear organopolysiloxane having a vinyl group (A) contain a first linear organopolysiloxane having a vinyl group (A1) containing 0.05% by mole to 0.2% by mole of a vinyl group, and a second linear organopolysiloxane having a vinyl group (A2) containing 0.5% by mole to 12% by mole of a vinyl group.
• the first linear organopolysiloxane having a vinyl group (A1) contain 0.1 to 0.15% by mole of a vinyl group
• the second linear organopolysiloxane having a vinyl group (A2) contain 0.8 to 8.0% by mole of a vinyl group.
• the ratio between the first linear organopolysiloxane having a vinyl group (A1) and the second linear organopolysiloxane having a vinyl group (A2) is not particularly limited.
• the weight ratio ((A1):(A2)) between them is preferably in a range of 1:0.05 to 1:0.6, in particular, 1:0.08 to 1:0.5 is more preferable.
• the linear organohydrogen polysiloxane (B) has a linear structure and a structure ( ⁇ Si—H) in which Si is directly connected with hydrogen.
• the linear organohydrogen polysiloxane (B) causes a hydrosilylation reaction with a vinyl group in a component added in the silicone rubber-based hardening composition to make a crosslink, in addition to the vinyl group in the linear organopolysiloxane having a vinyl group (A).
• the amount of the hydrogen atom which is directly bonded with Si is not particularly limited.
• the amount of the hydride group in the linear organohydrogen polysiloxane (B) is preferably in a range of 0.5 to 5 moles, and more preferably in a range of 1 to 3.5 moles relative to 1 mole of the vinyl group in the linear organopolysiloxane having a vinyl group (A).
• the molecular weight of the linear organohydrogen polysiloxane (B) is not particularly limited. However, the weight average molecular weight of the linear organohydrogen polysiloxane (B) is preferably 20,000 or less, and in particular, 7,000 is more preferable. The weight average molecular weight of the linear organohydrogen polysiloxane (B) can be measured by using GPC (Gel Permeation Chromatography).
• the linear organohydrogen polysiloxane (B) do not contain a vinyl group, because there is a possibility that the crosslinking reaction may be promoted in the molecule thereof.
• the linear organohydrogen polysiloxane (B) have a structure represented by the following formula (2).
• m denotes an integer from 0 to 300; n denotes an integer represented by (300 ⁇ m); R 4 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group; R 5 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group; at least two of plural R 4 and R 5 are a hydride group; and R 6 denotes an alkyl group, aryl group, which contains 1 to 8 carbon atoms, and has a substituted group or no substituted group, or a hydrocarbon group in which these groups are combined.
• R 4 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group.
• alkyl group which contains 1 to 10 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these alkyl groups, a methyl group is preferable.
• Examples of the alkenyl group which contains 1 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Among these alkenyl groups, a vinyl group is preferable.
• the aryl group which contains 1 to 10 carbon atoms include a phenyl group.
• R 5 denotes an alkyl group, alkenyl group, aryl group, which contains 1 to 10 carbon atoms, and has a substituted group or no substituted group, a hydrocarbon group in which these groups are combined, or a hydride group.
• alkyl group which contains 1 to 10 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these alkyl groups, a methyl group is preferable.
• Examples of the alkenyl group which contains 1 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Among these alkenyl groups, a vinyl group is preferable.
• the aryl group which contains 1 to 10 carbon atoms include a phenyl group.
• plural R 4 are independent to each other, and may be the same or not.
• plural R 5 are independent to each other, and may be the same or not, similar to R 4 .
• At least two of plural R 4 and R 5 are a hydride group.
• R 6 is an alkyl group, aryl group, which contains 1 to 8 carbon atoms, and has a substituted group or no substituted group, or a hydrocarbon group in which these groups are combined.
• alkyl group which contains 1 to 8 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these alkyl groups, a methyl group is preferable.
• aryl group which contains 1 to 8 carbon atoms include a phenyl group.
• Plural R 6 are independently, and may be the same or not.
• Examples of the substituted group in R 4 , R 5 , and R 6 which have a substituted group in the formula (2) include a methyl group, and a vinyl group.
• a methyl group is preferable because a methyl group can prevent the crosslinking reaction in the molecule.
• n and n are the number of repeating units that constitute the linear organohydrogen polysiloxane (B) represented by the formula (2), m is an integer from 0 to 300, and n is an integer from (300 ⁇ m). m is preferably in a range of 0 to 150, and n is preferably in a range of (150 ⁇ m).
• the linear organohydrogen polysiloxane (B) may be used alone or in combination of two or more.
• the trimethylsilyl group-surface treated silica filler (C) is silica filler of which the surface is treated with a silane coupling agent having a trimethylsilyl group [(CH 3 ) 3 —Si—] (this may be simply denoted by “trimethylsilyl group containing coupling agent”) in advance.
• the surface treatment of the silica filler with the silane coupling agent having a trimethylsilyl group means a treatment in which the hydroxyl group bonded with a silicon atom (silanol group: Si—OH) on the surface of the silica filler is replaced with a functional group containing a trimethylsilyl group derived from the silane coupling agent having a trimethylsilyl group, or a treatment in which a functional group containing a trimethylsilyl group derived from the silane coupling agent having a trimethylsilyl group is applied on the surface of the silica filler.
• the silane coupling agent having a trimethylsilyl group has a functional group containing a trimethylsilyl group and a hydrolyzable group. Under conditions in which hydrolysis can be carried out, the hydrolyzable group is hydrolyzed and a hydroxyl group is generated.
• the functional group containing a trimethylsilyl group means a trimethylsilyl group itself or a group containing a trimethylsilyl group as a part thereof.
• the silane coupling agent having a trimethylsilyl group typically has a structure in which a silicon atom in the trimethylsilyl group is bonded with the hydrolyzable group. Under conditions in which hydrolysis can be carried out, the hydrolyzable group is hydrolyzed and a silanol, in which the silicon atom in the trimethylsilyl group is bonded with the hydroxyl group, is generated.
• the hydroxyl group (typically silanol), which is generated by the hydrolysis of the hydrolyzable group in the silane coupling agent having a trimethylsilyl group, makes a dehydration condensation reaction with the hydroxyl group on the surface of the silica filler.
• the functional group containing a trimethylsilyl group of the silane coupling agent is covalently bonded with the silicon atom of the silica filler via an oxygen atom (O).
• O oxygen atom
• the silicon atom of the trimethylsilyl group in the silane coupling agent and the silicon atom in the silica filler make a covalent bond via an oxygen atom (O).
• the hydroxyl group of the silanol group on the surface of the silica filler is replaced with the functional group containing a trimethylsilyl group.
• silica filler of which the surface is treated with the silane coupling agent having a trimethylsilyl group examples include dried silica and wet silica.
• dried silica is preferable from the viewpoint of extrusion moldability of the silicone rubber, and fumed silica is more preferable.
• silane coupling agent having a trimethylsilyl group can be used as long as it has a trimethylsilyl group and generates a hydroxyl group under conditions in which hydrolysis can be carried out, and has a hydrolyzable group which can cause a dehydration condensation reaction with the hydroxyl group in the silanol group on the surface of the silica filler.
• silane coupling agent having a trimethylsilyl group include silazane, chlorosilane and alkoxysilane.
• silazane can be used as long as it has a structure in which the silicon atom in the trimethylsilyl group is bonded with a nitrogen atom.
• examples of the silazane used include hexamethyldisilazane.
• chlorosilane can be used as long as it has a structure in which the silicon atom in the trimethylsilyl group is bonded with a chlorine atom.
• chlorosilane used include trimethylchlorosilane.
• alkoxysilane can be used as long as it has a structure in which the silicon atom in the trimethylsilyl group is bonded with an alkoxy group.
• alkoxysilane used include trimethylmethoxysilane, and trimethylethoxysilane.
• At least one selected from the group consisting of hexadimethyldisilazane, trimethylchlorosilane, trimethylmethoxysilane, and trimethylethoxysilane is preferably used.
• the degree of the surface treatment of the silica filler with the silane coupling agent having a trimethylsilyl group is not particularly limited because a preferable degree varies depending on the kind of the silane coupling agent used, the surface area of the silica filler, and the like.
• the surface treatment is preferably carried out at a certain degree so that the trimethylsilyl group-surface treated silica filler (C) after the surface treatment contains 0.1 to 7.0% by weight, preferably 1.0 to 4.0% by weight, and more preferably 1.5 to 3.0% by weight of carbon atom.
• the carbon content in the trimethylsilyl group-surface treated silica filler (C) is relevant to the carbon content in organic groups derived from the silane coupling agent which is chemically bonded with the surface of the silica filler.
• the carbon content gives an indication of the surface treatment degree of the silica filler by the silane coupling agent.
• the carbon content of the trimethylsilyl group-surface treated silica filler (C) can be calculated in the following manner.
• the carbon content can be calculated by thermally decomposing the trimethylsilyl group-surface treated silica filler (C) under oxygen atmosphere at 1,000 to 1,200° C. using a trace carbon analyzer, and measuring the amount of CO 2 generated.
• Any surface treatment methods using the silane coupling agent having a trimethylsilyl group can be used without limitations.
• a method disclosed in Published Japanese Translation No. 2007-526373 of the PCT International Publication can be used.
• a method in which after spraying water to the silica filler (non-treated silica filler), of which the surface is not treated with the silane coupling agent having a trimethylsilyl group, the silane coupling agent having a trimethylsilyl group is also sprayed to the silica filler, and then the silica filler is thermally treated can be used.
• the water used may be acidified (for example, pH 1 to 7) using an acid such as hydrochloric acid.
• the silane coupling agent used may be dissolved in an appropriate solvent if necessary.
• the spraying of water or the silane coupling agent can be carried out using a one-fluid nozzle, two-fluid nozzle, or ultrasonic nozzle. It is preferable that the spraying be carried out in a vessel provided with a mixing means while stirring the silica filler. After spraying of water and the silane coupling agent, if necessary, the silica filler and water and/or the silica coupling agent may be mixed.
• the temperature and the time in the thermal treatment can be adjusted, and for example, the thermal treatment may be carried out at 20 to 400° C. for 0.1 to 6 hours.
• the thermal treatment can also be carried out under inert gas atmosphere such as nitrogen gas.
• a method in which the non-treated silica filler is subjected to the vapor of the silane coupling agent, and then heated (for example, 50 to 800° C.), can also be used.
• the thermal treatment can also be carried out under inert atmosphere.
• the trimethylsilyl group-surface treated silica filler (C) have a specific surface area of 30 m 2 /g or more, more preferably 100 m 2 /g or more, and 500 m 2 /g or less, and more preferably 300 m 2 /g or less.
• the specific surface area is most preferably in a range of 30 to 500 m 2 /g.
• the specific surface area of the trimethylsilyl group-surface treated silica filler (C) can be measured by a common method, for example, BET specific surface area method can be used.
• the average primary particle diameter of the trimethylsilyl group-surface treated silica filler (C) be 100 nm or less, and in particular, 20 nm or less is preferable.
• the average primary particle diameter of the trimethylsilyl group-surface treated silica filler (C) can be measured by a common method.
• the trimethylsilyl group-surface treated silica filler (C) can be used alone or in combination of two or more.
• the silica fillers (C), of which the surface is treated with different silane coupling agent having a trimethylsilyl groups, may be combined.
• the silicone rubber-based hardening composition according to the present invention may contain components in addition to the components (A) to (C).
• the component which may be added in addition to the components (A) to (C) platinum or a platinum compound (E), which is explained below, can be used.
• Platinum or a platinum compound (E) acts a catalyst for vulcanization.
• the amount used is a catalyst amount.
• platinum or a platinum compound (E) well-known components can be used.
• the platinum or the platinum compound (E) used include platinum black, a support in which platinum is supported on silica or carbon black, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a complex of chloroplatinic acid and olefin, and a complex of chloroplatinic acid and vinylsiloxane.
• the platinum or a platinum compound (E), which is a catalyst component may be used alone or in combination of two or more.
• the silicone rubber-based hardening composition according to the present invention may contain a well-known component which is added in the silicone rubber-based hardening composition in addition to the components (A) to (C), and (E).
• a well-known component which is added in the silicone rubber-based hardening composition in addition to the components (A) to (C), and (E).
• the component include diatom earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, cerium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, glass-wool, and mica.
• a dispersant, pigment, die, antistatic agent, antioxidant, flame retardant, heat conduction improver An appropriate amount of these components can be added in the silicone rubber-based hardening composition according to the present invention.
• the content of each component is not particularly limited. However, in general, it is preferable that the silicone rubber-based hardening composition contain 0.1 to 5 parts by weight of the linear organohydrogen polysiloxane (B), and 20 to 150 parts by weight of the trimethylsilyl group-surface treated silica filler (C), relative to 100 parts by weight of the linear organopolysiloxane having a vinyl group (A).
• the silicone rubber-based hardening composition contain 0.1 to 2 parts by weight of the linear organohydrogen polysiloxane (B), and 50 to 100 parts by weight of the trimethylsilyl group-surface treated silica filler (C), relative to 100 parts by weight of the linear organopolysiloxane having a vinyl group (A).
• the amount of platinum or the platinum compound (E) used is a catalyst amount, and can be appropriately adjusted.
• the content of platinum or the platinum compound (E) is preferably in a range of 0.05 to 5 parts by weight, and more preferably in a range of 0.1 to 1 part by weight relative to 100 parts by weight of the linear organopolysiloxane having a vinyl group (A).
• the silicone rubber-based hardening composition according to the present invention can be obtained by uniformly mixing the components explained above using a kneading device.
• a kneading device examples include kneader, two-roller, Banbury mixer (continuous kneader), and pressurized kneader.
• Platinum or the platinum compound (E) which is a catalyst is preferably dispersed in the linear organopolysiloxane having a vinyl group (A) from the viewpoint of ease of handling.
• the silicone rubber can be obtained by heating the silicone rubber-based hardening composition according to the present invention which is obtained as explained above at 140 to 180° C. for 5 to 15 minutes (first hardening), and then post-baking at 200° C. for 4 hours (second hardening).
• the silicone rubber which is excellent in the tear strength and tensile strength, in particular, tear strength, can be obtained by hardening the silicone rubber-based hardening composition according to the present invention.
• the silicone rubber which has 1,000% or more of an elongation at breaking (strain) of a dumb-bell shaped third test piece according to JIS K 6251 (2004), can be obtained by hardening the silicone rubber-based hardening composition according to the present invention.
• the silicone rubber having high elongation even when the silicone rubber contains a large amount of the silica filler can be obtained.
• the silicone rubber which can extend at 100 mm or more before breaking a crescent-shaped test piece according to JIS K 6252 (2001), can be obtained.
• the silicone rubber having high elongation even when the silicone rubber contains a large amount of the silica filler can be obtained.
• the tensile strength and elongation at breaking are based on JIS K 6251 (2004) except that the thickness of the test piece which is obtained by hardening the silicone rubber-based hardening composition is adjusted to 1 mm.
• the tear strength and stroke are based on JIS K 6252 (2001) except that the thickness of the test piece which is obtained by hardening the silicone rubber-based hardening composition is adjusted to 1 mm.
• the molded articles having excellent mechanical strength explained above can be obtained by using the silicone rubber having such tensile strength and tear strength.
• the medical tube for example, catheter
• the medical tube made of silicone rubber which is excellent in kink resistance and scratch resistance by using the molded article.
• the silicone rubber-based hardening composition preferably further contains silica filler (D), of which the surface is treated with a silane coupling agent having an organosilyl group containing a vinyl group.
• silica filler is often added in the silicone based hardening composition.
• the balance between the tensile strength, tear strength, and hardness could be remarkably improved by adding two kinds of silica filler in combination of which the surface is treated with a specific silica coupling agent in silicone rubber containing a specific matrix containing the linear organopolysiloxane having a vinyl group (A), and the linear organohydrogen polysiloxane (B) as raw material.
• the present inventors found that the mechanical strength, in particular, the balance between the tensile strength, tear strength, and hardness of silicone rubber could be improved by combining the linear organopolysiloxane having a vinyl group (A) and the linear organohydrogen polysiloxane (B); and the silica filler (C) (this may be simply denoted by “silicon filler (C)” below) of which the surface is treated with a silane coupling agent having a trimethylsilyl group in advance, and silica filler (D) of which the surface is treated with a silane coupling agent having an organosilyl group containing a vinyl group (this may be simply denoted by “silicon filler (D)” below).
• these demerits due to the silica filler can be solved and properties of the silicone rubber can be improved by using both of the silica filler (C) of which the surface is treated with a silane coupling agent having a trimethylsilyl group in advance, and the silica filler (D) of which the surface is treated with a silane coupling agent having an organosilyl group containing a vinyl group.
• the silica filler (C) has high hydrophobic properties because the surface of the silica filler (C) is previously treated with the silane coupling agent having a trimethylsilyl group.
• the cohesive force of the silica filler (C) is decreased (condensation due to the hydrogen bond by the silanol group is decreased) in the silicone rubber-based hardening composition containing the linear organopolysiloxane having a vinyl group (A), and the linear organohydrogen polysiloxane (B) is decreased, and thereby, the dispersibility of the silica filler (C) in the composition is improved.
• the interface between the silica filler (C) and the rubber matrix is increased by improving the dispersibility of the silica filler (C), and the rubber molecular chains, which are affected by the silica filler, are increased.
• the molecular mobility of the rubber molecular chains, which are affected by the silica filler is decreased by the interaction with the silica filler.
• the rubber molecular chain is hard compared with an area having high molecular mobility.
• the tear behavior in silicone rubber when an initial crack grows and spreads, and tear stress is applied to the hard area, the hard area resists the tear stress. As a result, the tear strength is increased.
• the silica filler (D) is previously subjected to a surface treatment using a silane coupling agent having an organosilyl group containing a vinyl group. Therefore, the surface of the silica filler (D) has a vinyl group.
• the vinyl group becomes a crosslinking point when vulcanization is carried out.
• a covalent bond is generated between the silica filler (D) and a matrix containing the linear organopolysiloxane having a vinyl group (A) and the linear organohydrogen polysiloxane (B) in the silicone rubber obtained by hardening the silicone rubber-based hardening composition according to this embodiment. Because of the reason as presumed above, the hardness can be improved while maintaining high tear strength of the silicone rubber by forming a rubber matrix-silica filler network in the silicone rubber.
• the silicone rubber which is obtained by hardening the silicone rubber-based hardening composition in this embodiment has excellent tear strength and hardness. Therefore, it is possible to obtain the catheter made of the silicone rubber which is excellent in kink resistance, scratch resistance, and ease of insertion by using the silicone rubber-based hardening composition according to this embodiment.
• the surface of the silica filler (D) is treated with a silane coupling agent having an organosilyl group containing a vinyl group in advance.
• the surface treatment of the silica filler with the silane coupling agent having an organosilyl group containing a vinyl group means a treatment in which the hydroxyl group bonded with a silicon atom (silanol group: Si—OH) on the surface of the silica filler is replaced with a functional group containing an organosilyl group containing a vinyl group derived from the silane coupling agent having an organosilyl group containing a vinyl group, or a treatment in which an organosilyl group containing a vinyl group derived from the silane coupling agent having an organosilyl group containing a vinyl group is applied on the surface of the silica filler.
• the silane coupling agent having an organosilyl group containing a vinyl group has a functional group containing an organosilyl group containing a vinyl group and a hydrolyzable group. Under conditions in which hydrolysis can be carried out, the hydrolyzable group is hydrolyzed and a hydroxyl group is generated.
• the organosilyl group containing a vinyl group means a group (CH 2 ⁇ CH—Si ⁇ ) in which at least one vinyl group is directly bonded with a silicon atom or a group (CH 2 ⁇ CH—W—Si ⁇ ) in which at least one vinyl group is bonded with a silicon atom via a linking group W.
• the linking group W include an alkyl group, ether group, and ester group.
• the functional group containing an organosilyl group containing a vinyl group means an organosilyl group containing a vinyl group itself or a group containing an organosilyl group containing a vinyl group as a part thereof.
• the silane coupling agent having an organosilyl group containing a vinyl group typically has a structure in which a silicon atom in the organosilyl group containing a vinyl group is bonded with at least one hydrolyzable group. Under conditions in which hydrolysis can be carried out, the hydrolyzable group is hydrolyzed and a silanol, in which the silicon atom in the organosilyl group containing a vinyl group is bonded with the at least one hydroxyl group, is generated.
• the hydroxyl group (typically silanol), which is generated by the hydrolysis of the hydrolyzable group in the silane coupling agent having an organosilyl group containing a vinyl group, makes a dehydration condensation reaction with the hydroxyl group on the surface of the silica filler.
• the functional group containing the organosilyl group containing a vinyl group of the silane coupling agent is covalently bonded with the silicon atom of the silica filler via an oxygen atom (O).
• O oxygen atom
• the silicon atom of the organosilyl group containing a vinyl group in the silane coupling agent and the silicon atom in the silica filler make a covalent bond via an oxygen atom (O).
• the hydroxyl group of the silanol group on the surface of the silica filler is replaced with the functional group containing the organosilyl group containing a vinyl group.
• silica filler of which the surface is treated with the silane coupling agent having an organosilyl group containing a vinyl group examples include dried silica and wet silica.
• dried silica is preferable from the viewpoint of extrusion moldability of the silicone rubber, and fumed silica is more preferable.
• silane coupling agent having an organosilyl group containing a vinyl group can be used as long as it has an organosilyl group containing a vinyl group and generates a hydroxyl group under conditions in which hydrolysis can be carried out, and has a hydrolyzable group which can cause a dehydration condensation reaction with the hydroxyl group in the silanol group on the surface of the silica filler.
• silane coupling agent having an organosilyl group containing a vinyl group include silazane, chlorosilane and alkoxysilane.
• silazane can be used as long as it has a structure in which the silicon atom in the organosilyl group containing a vinyl group is bonded with at least one nitrogen atom.
• examples of the silazane used include divinyltetramethyldisilazan.
• chlorosilane can be used as long as it has a structure in which the silicon atom in the organosilyl group containing a vinyl group is bonded with at least one chlorine atom.
• chlorosilane used include vinyltrichlorosilane.
• alkoxysilane can be used as long as it has a structure in which the silicon atom in the organosilyl group containing a vinyl group is bonded with at least one alkoxy group.
• alkoxysilane used include methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyltriethoxysilanne, vinyltrimethoxysilane, and vinylmethyldimethoxysilane.
• silica filler (D) it is preferable that all of the hydroxyl group in the silanol group on the surface of the silica filler (D) be replaced with the functional group containing an organosilyl group containing a vinyl group derived from the silane coupling agent having an organosilyl group containing a vinyl group.
• silane coupling agent having an organosilyl group containing a vinyl group can be used without limitations.
• silica filler is put in a mixer, first, water and then the silane coupling agent having an organosilyl group containing a vinyl group, such as methacryloxypropyltriethoxysilane are added in the silica filler while stirring, they are mixed at 30° C. for 15 minutes, dried in an oven at 100° C. for about 1 hour, and then cooled.
• silane coupling agent having an organosilyl group containing a vinyl group such as methacryloxypropyltriethoxysilane
• the silica filler (D) have a specific surface area of 30 m 2 /g or more, more preferably 100 m 2 /g or more, and 500 m 2 /g or less, and more preferably 300 m 2 /g or less.
• the specific surface area is most preferably in a range of 30 to 500 m 2 /g.
• the specific surface area of the silica filler (D) can be measured by a common method, for example, BET specific surface area method can be used.
• the average primary particle diameter of the silica filler (D) be 100 nm or less, and in particular, 20 nm or less is preferable.
• the average primary particle diameter of the silica filler (D) can be measured by a common method.
• the silica filler (D) can be used alone or in combination of two or more.
• the silica fillers (D) of which the surface is treated with a different silane coupling agent having an organosilyl group containing a vinyl group, may be combined.
• the content of each component is not particularly limited.
• the silicone rubber-based hardening composition contain 0.1 to 5 parts by weight of the linear organohydrogen polysiloxane (B), 20 to 150 parts by weight of the silica filler (C), and 0.5 to 100 parts by weight of the silica filler (D), relative to 100 parts by weight of the linear organopolysiloxane having a vinyl group (A).
• the silicone rubber-based hardening composition contain 0.1 to 2 parts by weight of the linear organohydrogen polysiloxane (B), 40 to 100 parts by weight of the silica filler (C), and 0.5 to 50 parts by weight of the silica filler (D), relative to 100 parts by weight of the linear organopolysiloxane having a vinyl group (A).
• silicone rubber having a type A-durometer hardness according to JIS K 6253 (2006) of 55 or more by hardening the silicone rubber-based hardening composition according to this embodiment.
• the type A-durometer hardness is preferably 55 or more, and in particular 58 or more is preferable.
• a molded article having excellent mechanical strength can be obtained by using the silicone rubber having such hardness.
• the medical tube for example, catheter
• the medical tube made of silicone rubber, which is excellent in mechanical strength, such as ease of insertion, can also be obtained by using the molded article.
• the silicone rubber which has long elongation (strain) at break of a dumb-bell shaped third test piece according to JIS K 6251 (2004) or long elongation (stroke) before breaking a crescent-shaped test piece according to JIS K 6252 (2001), can be obtained by hardening the silicone rubber-based hardening composition according to this embodiment.
• the tear strength and stroke are based on JIS K 6252 (2001) except that the thickness of the test piece which is obtained by hardening the silicone rubber-based hardening composition is adjusted to 1 mm.
• the type A durometer hardness is based on JIS K 6253 (2006), and can be measured using the test piece which is obtained by hardening the silicone rubber-based hardening composition.
• the tensile strength and elongation at breaking are based on JIS K 6251 (2004) except that the thickness of the test piece which is obtained by hardening the silicone rubber-based hardening composition in this embodiment is adjusted to 1 mm.
• (A1) first linear organopolysiloxane containing a vinyl group, the content of a vinyl group: 0.13% by mole, and this was synthesized by the following synthesis scheme.
• (C1) silica filler of which the surface is treated with hyxamethyldisilazane made of Nippon Aerosil Co., Ltd., trade name: Aerosil® RX200, specific surface area: 200 m 2 /g; average primary particle diameter: 12 nm; and carbon content: 2.5% by weight
• (C2) silica filler of which the surface is treated with hyxamethyldisilazane made of Nippon Aerosil Co., Ltd., trade name: Aerosil® RX300, specific surface area: 300 m 2 /g; average primary particle diameter: 7 nm; and carbon content: 3.5% by weight
• (c1) silica filler of which the surface is not treated made of Nippon Aerosil Co., Ltd., trade name: Aerosil® 200, specific surface area: 200 m 2 /g; and average primary particle diameter: 12 nm
• (c2) silica filler of which the surface is treated with dimethyldichlorosilane made of Nippon Aerosil Co., Ltd., trade name: Aerosil® R972, specific surface area: 130 m 2 /g; and average primary particle diameter: 16 nm
• the first linear organopolysiloxane containing a vinyl group (A1) was synthesized.
• the product was diluted with 250 mL of toluene, and washed with water 3 times. After washing, the organic phase was reprecipitated by washing with 1.5 L of methanol several times and purified to separate an oligomer and a polymer.
• the obtained polymer was dried at 60° C. under reduced pressure overnight, and the first linear organopolysiloxane containing a vinyl group (A1) (Mn: 277, 734; Mw: 573, 906; IV value (dl/g): 0.89) was produced.
• the second linear organopolysiloxane containing a vinyl group (A2) was synthesized in a manner identical to that of the first linear organopolysiloxane containing a vinyl group (A1) except that 0.86 g (2.5 mmol) of 2,4,6,8-tetramethyl 2,4,6,8-tetravinylcyclotetrasiloxane was used.
• silica filler (C1) 50 parts by weight of the silica filler (C1) was added in 100 parts by weight of the first linear organopolysiloxane having a vinyl group (A1), and kneaded to prepare a master batch.
• the weight ratio of the raw material used is shown in Table 1.
• the prepared silicone rubber-based hardening composition was pressed at 170° C. for 10 minutes with 10 mPA to mold a sheet having a thickness of 1 mm, and primarily hardened.
• the obtained sheet was heated at 200° C. for 4 hours, and secondarily hardened.
• a crescent-shaped test piece was produced based on JIS K 6252 (2001) using the obtained silicone rubber in a sheet shape. Then, the tear strength and the elongation (stroke) until breaking of the crescent-shaped test piece were measured according to JIS K 6252 (2001). Moreover, the thickness of the test piece was 1 mm. The results are shown in Table 1.
• the prepared silicone rubber-based hardening composition was pressed at 170° C. for 10 minutes with 10 MPa to mold a sheet having a thickness of 1 mm, and primarily hardened.
• the obtained sheet was heated at 200° C. for 4 hours, and secondarily hardened.
• a dumb-bell shaped third test piece was produced based on JIS K 6251 (2004) using the obtained silicone rubber in a sheet shape. Then, the tensile strength and the elongation (strain) at break of the dumb-bell shaped third test piece were measured according to JIS K 6251 (2004). Moreover, the thickness of the test piece was 1 mm. The results are shown in Table 1.
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 1, except that the content of the silica filler (C) was changed to 7.0 parts by weight.
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 2, except that the silica filler (C2) was used instead of the silica filler (C1).
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 3, except that the silica filler (C2) was used instead of the silica filler (C1).
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 1, except that 33 parts by weight of the silica filler (c1) was used instead of 50 parts by weight of the silica filler (C1).
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 1, except that the content of the silica filler (c2) was used instead of the silica filler (C1).
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 1, except that the content of the silica filler (c3) was used instead of the silica filler (C1).
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 1, except that 70 parts by weight of the silica filler (c3) was used instead of 50 parts by weight of the silica filler (C1).
• the silicone rubber which is obtained by hardening the silicone rubber-based hardening composition containing the silica filler (C1) or (C2) of which the surface is treated with the silane coupling agent having a trimethylsilyl group has 28 N/nn or more of the tear strength, and 7.5 MPa or more of tensile strength.
• the silicone rubber is excellent in the tear strength and the tensile strength.
• the tear strength of the silicone rubber obtained in Examples 1 to 5 is remarkably improved compared with the tear strength of the silicone rubber obtained in Comparative Examples 1 to 4 which contains the silica filler (c1) to (c3) of which the surface is not treated with the silane coupling agent having a trimethylsilyl group.
• the reason for the large decrease of tear strength is considered to be because the surface of the silica filler (c3) is treated with dimethyldichlorosilane, and therefore, the silica filler (c3) has higher cohesive force compared with the silica filler (C) of which the surface is treated with the silane coupling agent having a trimethylsilyl group.
• the silica filler (c3) When a large amount of the silica filler (c3) is added, the elongation of the silicone rubber is remarkably decreased, and because of this, the silicone rubber easily reaches a breaking point, and the tear strength is decreased.
• the surface of the silica filler (C) used in Examples is treated with the silane coupling agent having a trimethylsilyl group, and therefore the silica filler has lower cohesive force.
• the molecular chains of the silicone rubber easily slip. Therefore, even when a large amount of the silica filler is added, the decrease of elongation of the silicone rubber is small. Due to this, sufficient stiffening effects due to the silica filler can be obtained.
• (A1) first linear organopolysiloxane containing a vinyl group, the content of a vinyl group: 0.13% by mole, and this was synthesized by the following synthesis scheme.
• (C1) silica filler of which the surface is treated with hyxamethyldisilazane made of Nippon Aerosil Co., Ltd., trade name: Aerosil® RX200, specific surface area: 200 m 2 /g; average primary particle diameter: 12 nm; and carbon content: 2.5% by weight
• (C2) silica filler of which the surface is treated with hyxamethyldisilazane made of Nippon Aerosil Co., Ltd., trade name: Aerosil® RX300, specific surface area: 300 m 2 /g; average primary particle diameter: 7 nm; and carbon content: 3.5% by weight
• (D1) silica filler of which the surface is treated with methacryloxypropyltriethoxysilane, made of Nippon Aerosil Co., Ltd., trade name: Aerosil® R711, specific surface area: 200 m 2 /g; and average primary particle diameter: 12 nm
• silica filler of which the surface is treated with dimethyldichlorosilane, made of Nippon Aerosil Co., Ltd., trade name: Aerosil® R974, specific surface area: 200 m 2 /g; and average primary particle diameter: 12 nm
• the first linear organopolysiloxane containing a vinyl group (A1) was synthesized.
• the product was diluted with 250 mL of toluene, and washed with water 3 times. After washing, the organic phase was reprecipitated by washing with 1.5 L of methanol several times and purified to separate an oligomer and a polymer.
• the obtained polymer was dried at 60° C. under reduced pressure overnight, and the first linear organopolysiloxane containing a vinyl group (A1) (Mn: 277, 734; Mw: 573, 906; IV value (dl/g): 0.89) was produced.
• the second linear organopolysiloxane containing a vinyl group (A2) was synthesized in a manner identical to that of the first linear organopolysiloxane containing a vinyl group (A1) except that 0.86 g (2.5 mmol) of 2,4,6,8-tetramethyl 2,4,6,8-tetravinylcyclotetrasiloxane was used.
• the weight ratio of the raw materials used is shown in Table 2.
• the prepared silicone rubber-based hardening composition was pressed at 170° C. for 10 minutes with 10 MPa to mold a sheet having a thickness of 1 mm, and primarily hardened.
• the obtained sheet was heated at 200° C. for 4 hours, and secondarily hardened.
• a crescent-shaped test piece was produced based on JIS K 6252 (2001) using the obtained silicone rubber in a sheet shape. Then, the tear strength and the elongation (stroke) until breaking of a crescent-shaped test piece were measured according to JIS K 6252 (2001). Moreover, the thickness of the test piece was 1 mm. The results are shown in Table 2.
• the prepared silicone rubber-based hardening composition was pressed at 170° C. for 10 minutes with 10 MPa to mold a sheet having a thickness of 1 mm, and primarily hardened.
• the obtained sheet was heated at 200° C. for 4 hours, and secondarily hardened.
• a dumb-bell shaped third test piece was produced using the obtained silicone rubber in a sheet shape according to JIS K 6251 (2004). Then, the tensile strength and the elongation (strain) until breaking of the dumb-bell shaped third test piece were measured according to JIS K 6251 (2004). Moreover, the thickness of the test piece was 1 mm. The results are shown in Table 2.
• the prepared silicone rubber-based hardening composition was pressed at 170° C. for 10 minutes with 10 MPa to mold a sheet having a thickness of 1 mm, and primarily hardened. Then, the obtained sheet was heated at 200° C. for 4 hours, and secondarily hardened.
• test piece was produced using the obtained silicone rubber-based hardening composition, and evaluated. The results are shown in Table 2.
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 7, except that the content of the silica filler (C1) and the silica filler (D2) was changed to 60 parts by weight and 9 parts by weight respectively.
• test piece was produced using the obtained silicone rubber-based hardening composition, and evaluated. The results are shown in Table 2.
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 6, except that 70 parts by weight of the silica filler (C1) was used instead of 64.3 parts by weight of the silica filler (C1) and 5.4 parts by weight of the silica filler (D1).
• test piece was produced using the obtained silicone rubber-based hardening composition, and evaluated. The results are shown in Table 2.
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 7, except that 70 parts by weight of the silica filler (C2) was used instead of 66 parts by weight of the silica filler (C2) and 4.2 parts by weight of the silica filler (D2).
• test piece was produced using the obtained silicone rubber-based hardening composition, and evaluated. The results are shown in Table 2.
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 10, except that the silica filler (D1) was used instead of the silica filler (C2).
• test piece was produced using the obtained silicone rubber-based hardening composition, and evaluated. The results are shown in Table 2.
• the silicone rubber-based hardening composition was obtained in a manner identical to that of Example 10, except that the silica filler (f) was used instead of the silica filler (C2).
• test piece was produced using the obtained silicone rubber-based hardening composition, and evaluated. The results are shown in Table 2.
• the silicone rubber which is obtained by hardening the silicone rubber-based hardening composition containing the silica filler (C1) or (C2), and the silica filler (D1) or (D2) is excellent in the balance between the tear strength, tensile strength, and hardness compared with the silicone rubber in Examples 9 to 11 and Comparative Examples 5 and 6 which is obtained by hardening the silicone rubber-based hardening composition containing only the silica filler (C1), (C2), (D1), or (f).
• Example 6 Specifically, it can be understood by the comparison between Example 6 and Example 9, and comparison between Examples 7 and 8, and Example 10 that the silicone rubber in Examples 6 to 8 has improved hardness compared with the silicone rubber in Examples 9 and 10 which contains only the silica filler (C1) or (C2).
• Example 7 and 8 has remarkably improved tear strength and tensile strength in addition to the stroke and elongation at breaking, compared with the silicone rubber in Comparative Example 5 which contains only the silica filler (D1).
• Example 7 and 8 has remarkably improved tear strength, stroke, and elongation at breaking compared with the silicone rubber in Comparative Example 6 which contains only the silica filler (f), and does not contain both of the silica fillers (C) and (D).
• the silicone rubber obtained by hardening the silicone rubber-based hardening composition according to the present invention is excellent in mechanical strength such as tensile strength and tear strength, in particular, tear strength. Therefore, the molded article which is obtained by using the silicone rubber-based hardening composition and the medical tube which is obtained by using the molded article have high mechanical strength. In other words, according to the present invention, it is possible to produce a medical catheter made of silicone rubber which is excellent in scratch resistance and kink resistance, in particular, scratch resistance.
• the present invention is extremely industrially important.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Health & Medical Sciences (AREA)
• Epidemiology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Composite Materials (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Materials For Medical Uses (AREA)

Priority Applications (1)

Applications Claiming Priority (5)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=46720915

Family Applications (2)

Family Applications After (1)

Country Status (5)

Cited By (4)

Families Citing this family (23)

Citations (10)

Family Cites Families (29)

• 2012
  • 2012-02-22 US US14/001,093 patent/US20130331821A1/en not_active Abandoned
  • 2012-02-22 CN CN201280019998.9A patent/CN103492491B/zh active Active
  • 2012-02-22 EP EP12750080.9A patent/EP2679636A4/en not_active Withdrawn
  • 2012-02-22 JP JP2013501088A patent/JP5846196B2/ja active Active
  • 2012-02-22 WO PCT/JP2012/054250 patent/WO2012115139A1/ja active Application Filing
• 2015
  • 2015-10-09 US US14/879,685 patent/US9562158B2/en active Active
  • 2015-11-26 JP JP2015231115A patent/JP6065963B2/ja active Active

Patent Citations (10)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events