WO2024117187A1 - 付加硬化型液状シリコーン組成物保存用容器 - Google Patents

付加硬化型液状シリコーン組成物保存用容器 Download PDF

Info

Publication number
WO2024117187A1
WO2024117187A1 PCT/JP2023/042752 JP2023042752W WO2024117187A1 WO 2024117187 A1 WO2024117187 A1 WO 2024117187A1 JP 2023042752 W JP2023042752 W JP 2023042752W WO 2024117187 A1 WO2024117187 A1 WO 2024117187A1
Authority
WO
WIPO (PCT)
Prior art keywords
addition
liquid silicone
silicone composition
container
sealing structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/042752
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
寛保 原
志保 湯浅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Priority to KR1020257020076A priority Critical patent/KR20250117391A/ko
Priority to CN202380082130.1A priority patent/CN120282917A/zh
Priority to JP2024561540A priority patent/JPWO2024117187A1/ja
Priority to EP23897833.2A priority patent/EP4628423A1/en
Publication of WO2024117187A1 publication Critical patent/WO2024117187A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D51/00—Closures not otherwise provided for
    • B65D51/24—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes
    • B65D51/28—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes with auxiliary containers for additional articles or materials
    • B65D51/30—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes with auxiliary containers for additional articles or materials for desiccators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
    • B65D77/04—Articles or materials enclosed in two or more containers disposed one within another
    • B65D77/0406—Rigid containers in preformed flexible containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
    • B65D81/268—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants the absorber being enclosed in a small pack, e.g. bag, included in the package
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/76—Containers or packages with special means for dispensing contents for dispensing fluent contents by means of a piston
    • 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

Definitions

  • the present invention relates to a container for storing a curable liquid silicone composition (curable liquid silicone rubber composition or curable liquid silicone gel composition) that contains an aerobic platinum catalyst mixture that is activated as a hydrosilylation addition reaction catalyst by contact with moisture (humidity) and/or oxygen in the atmosphere and that can be cured to give a silicone rubber cured product (silicone elastomer elastic body) or a silicone gel cured product.
  • a curable liquid silicone composition curable liquid silicone rubber composition or curable liquid silicone gel composition
  • an aerobic platinum catalyst mixture that is activated as a hydrosilylation addition reaction catalyst by contact with moisture (humidity) and/or oxygen in the atmosphere and that can be cured to give a silicone rubber cured product (silicone elastomer elastic body) or a silicone gel cured product.
  • Liquid curing silicone compositions that are one-part and crosslinking reaction types that can be cured without heating include condensation reaction types, UV radical reaction types, and addition reaction types, and among these, there are some that have a significantly shorter shelf life or can be cured by activating a catalyst with UV light. However, all of these have insufficient deep curing properties or curing properties in dark areas where UV light does not reach, limiting the applications in which they can be used. Also, when UV light irradiation is required, a large amount of electrical energy is required for this purpose.
  • Patent Document 7 proposes a one-component, aerobically curable, addition-curable liquid silicone composition that remains in a liquid state in a sealed container that is substantially deoxygenated and dehydrated, and that can undergo reactive curing when the container is opened and exposed to the atmosphere.
  • the present invention has been made in consideration of the above circumstances, and aims to provide a storage container for addition-curing liquid silicone compositions that is one-part and aerobically curable, improving the storage stability of addition-curing liquid silicone compositions.
  • a container for storing an aerobically curable addition-curable liquid silicone composition is provided with a first sealing structure having a sealing portion in which the addition-curable liquid silicone composition is filled and the injection port for the composition is sealed, and a second sealing structure which further seals the sealing portion, and the gap between the first sealing structure and the second sealing structure is provided with deoxidizing and dehydrating functions, thereby making it possible to significantly improve the storage stability of the aerobically curable liquid silicone composition in the first sealing structure, particularly an addition-curable liquid silicone composition containing an aerobic platinum catalyst.
  • the present invention provides the following container (packaging form) for storing an addition-curable liquid silicone composition.
  • a container for storing an addition-curing liquid silicone composition which contains a platinum catalyst which is inactive in an atmosphere with a humidity of 5% RH or less and an oxygen concentration of 0.1% by volume or less and which is activated when exposed to air, and which crosslinks and cures by a hydrosilylation addition reaction in the presence of the platinum catalyst activated in air
  • the container for storing an addition-curable liquid silicone composition according to any one of [3] to [6], wherein the organosilicon compound having at least one hydrogen atom bonded to a silicon atom is one or more compounds selected from trialkoxy(hydrogen)silanes, alkyldialkoxy(hydrogen)silanes, dialkylalkoxy(hydrogen)silanes, 1,1,1,3,3-pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and 1,3,5,7,9-pentamethylcyclopentasiloxane.
  • the container for storing an addition-curable liquid silicone composition according to any one of [3] to [7], wherein the organosilicon compound having at least one hydrogen atom bonded to a silicon atom is an organohydrogensiloxane oligomer having in the molecule at least two hydrogen atoms (SiH groups) bonded to adjacent silicon atoms via oxygen atoms that form siloxane bonds (Si—O—Si).
  • the organosilicon compound having at least one hydrogen atom bonded to a silicon atom is an organohydrogensiloxane oligomer having in the molecule at least two hydrogen atoms (SiH groups) bonded to adjacent silicon atoms via oxygen atoms that form siloxane bonds (Si—O—Si).
  • the second sealing structure is made of a resin film.
  • [15] The container for storing an addition-curable liquid silicone composition according to any one of [1] to [14], wherein a member having a function of consuming and removing oxygen and moisture is provided in the space between the first sealing structure and the second sealing structure.
  • [16] The container for storing an addition-curable liquid silicone composition according to any one of [1] to [15], wherein a member having a function of consuming and removing oxygen and moisture is disposed on the sealing portion of the first sealing structure.
  • [17] The container for storing an addition-curable liquid silicone composition according to any one of [1] to [16], wherein the function of the component having the function of consuming and removing oxygen and moisture is to chemically react with and absorb oxygen and moisture in the space in which the component exists.
  • the storage container of the present invention can improve the preservability and storage properties of aerobic curing liquid silicone compositions, particularly one-part addition curing liquid silicone compositions containing a platinum catalyst mixture that is activated as a hydrosilylation addition reaction catalyst by contact with moisture (humidity) and/or oxygen in the air (i.e., materials that have sufficient "long-term one-part preservability in a sealed container” for storing and transporting materials at refrigeration to room temperature, and when the materials are used, they can be "activated in an unheated, open state (i.e., by contacting moisture (humidity) and/or oxygen in the air at room temperature), causing the aerobic platinum catalyst mixture contained in the composition to undergo a hydrosilylation addition reaction, and rapidly curing not only on the surface exposed to air, but also in the depths”), and can increase the flexibility of transportation, contributing to energy conservation and the supply of various parts and products in accordance with the SDGs.
  • moisture (humidity) and/or oxygen in the air i.e.
  • FIG. 1A and 1B are schematic diagrams showing the configuration of a can, which is a first embodiment of a container for storing an addition-curable liquid silicone composition according to the present invention, in which (a) is a configuration diagram of the entire container, and (b) is a cross-sectional view of a main part of this embodiment.
  • FIG. 2 is a schematic cross-sectional view showing the configuration of a cartridge which is a second embodiment of a container for storing an addition-curable liquid silicone composition according to the present invention.
  • FIG. 1A and 1B are schematic diagrams showing the configuration of a can, which is a first embodiment of a container for storing an addition-curable liquid silicone composition according to the present invention, in which (a) is a configuration diagram of the entire container, and (b) is a cross-sectional view of a main part of this embodiment.
  • FIG. 2 is a schematic cross-sectional view showing the configuration of a cartridge which is a second embodiment of a container for storing an addition-curable liquid
  • FIG. 1 is a schematic diagram showing the configuration of a package (1), which is a third embodiment of a container for storing an addition-curable liquid silicone composition according to the present invention, in which (a) is a diagram showing the configuration before sealing with a second sealing structure, and (b) is a diagram showing the configuration after sealing with the second sealing structure.
  • FIG. 1 is a schematic diagram showing the configuration of a package (2) which is a fourth embodiment of a container for storing an addition-curable liquid silicone composition according to the present invention.
  • "aerobic” refers to the property (aerobic reaction type) of a catalyst (particularly a platinum catalyst) that is activated as a hydrosilylation addition reaction catalyst by contact with moisture (humidity) and/or oxygen in the air, when the catalyst has low catalytic activity as a hydrosilylation addition reaction catalyst in a sealed state with a low oxygen concentration (substantially no oxygen) and low moisture content, where contact with moisture (humidity) and oxygen is blocked
  • "aerobic curing” refers to the property of an addition-curing liquid silicone composition in which the hydrosilylation addition reaction does not proceed (does not cure) in a sealed state with a low oxygen concentration and low moisture content, where contact with moisture (humidity) and oxygen is blocked by such an aerobic catalyst, but the hydrosilylation addition reaction is promoted and the composition cures when the composition comes into contact with the air.
  • a sealed state refers to a state in which contact with the air is blocked (i.e., contact with moisture (humidity) and oxygen is blocked)
  • a sealed container refers to a container that realizes this sealed state.
  • the "atmosphere" referred to here is based on an oxygen concentration of 21% by volume and a humidity of more than 5% RH and 100% RH or less.
  • a low oxygen concentration in a sealed state is an oxygen concentration of 0.1% by volume or less, and a low moisture content is a humidity of 5% RH or less.
  • the addition-curing liquid silicone composition to be preserved in the present invention is an addition-curing liquid silicone composition that is inactive in an atmosphere with a humidity of 5% RH or less and an oxygen concentration of 0.1% by volume or less, contains a platinum catalyst that is activated when exposed to air, and crosslinks and cures by a hydrosilylation addition reaction in the presence of the platinum catalyst activated in the air, a so-called aerobic curing addition-curing liquid silicone composition, and is preferably, for example, the composition shown in Patent Document 7.
  • the activity of the platinum catalyst which is a curing reaction catalyst, is low, and the composition does not cure and remains liquid, but when exposed to the air, the platinum catalyst is activated by the oxygen and/or moisture in the air, and crosslinking and curing proceeds rapidly by a hydrosilylation addition reaction, allowing the desired cured product (cured silicone rubber, cured silicone gel, etc.) to be obtained.
  • Similar curable silicone compositions include condensation-curable silicone compositions that react and cure with moisture from the atmosphere. In this case, there are various methods for improving the shelf life of condensation-curable silicone compositions by preventing the intrusion of moisture from the outside air. However, since the curing properties of such condensation-curable silicone compositions are not affected by oxygen, preventing the intrusion of oxygen has not been considered as a method for improving shelf life, and these methods have been insufficient as a means for packaging the aerobically curable addition-curable liquid silicone composition that is the subject of the present invention.
  • the prepared composition in order to carry out the rational production of an aerobic curing addition-curing liquid silicone composition, the prepared composition must be quickly filled into a filling container and then sealed in the filling container.
  • the filling port into which the addition-curing liquid silicone composition is poured is sealed by inserting, fitting or screwing a lid into the filling port, or by gluing or heat fusing the filling port itself, but the material and structure of the sealed part (sealing part), particularly the structure in which the lid is inserted, fitted or screwed, cannot completely prevent the intrusion of oxygen and moisture from the outside air at the sealing part.
  • the above-mentioned filled container as a first sealing structure, and covering at least the entire sealing portion of the first sealing structure or the entire first sealing structure with a second sealing structure (film) to further seal, and additionally providing a member having the function of consuming and removing oxygen and moisture (a mechanism for removing oxygen and moisture) between the first sealing structure and the second sealing structure (gap), it was found that it was possible to virtually eliminate the intrusion of oxygen and moisture from the outside air into the addition-curable liquid silicone composition inside the container, and thus the container for storing addition-curable liquid silicone composition of the present invention was completed.
  • the container for storing an addition-curable liquid silicone composition of the present invention is a container for storing an addition-curable liquid silicone composition which is inactive in an atmosphere with a humidity of 5% RH or less and an oxygen concentration of 0.1% by volume or less, contains a platinum catalyst which is activated when exposed to air, and which crosslinks and cures by a hydrosilylation addition reaction in the presence of the platinum catalyst activated in air, (1) A first sealing structure which is a container into which the addition-curable liquid silicone composition is sealed (filled), the first sealing structure having a sealing part formed by sealing an injection port through which the addition-curable liquid silicone composition is injected; (2) a second sealing structure that is a film that covers at least the entire sealing portion of the first sealing structure or the entire first sealing structure to further seal the sealing portion; (3) A member having a function of consuming and removing oxygen and moisture is provided between the first sealing structure and the second sealing structure.
  • the first sealing structure is a container in which the addition-curing liquid silicone composition is sealed, and is preferably made of a metal, glass, ceramic, or resin container.
  • Metals constituting the first sealing structure include aluminum, iron, stainless steel, etc., ceramics include alumina, etc., and resins include synthetic resins such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride.
  • the first sealing structure only needs to have a thickness that ensures the strength required for the first sealing structure and prevents the passage of air (i.e., oxygen and moisture).
  • the container form of the first sealing structure can be selected from among cans, bottles, tubes, cartridges, etc., depending on the physical properties (viscosity, etc.) of the addition-curing liquid silicone composition to be filled and the intended use (mode of use).
  • the first sealing structure has a sealing portion formed by sealing the injection port through which the addition-curing liquid silicone composition is injected. That is, the container of the first sealing structure is initially provided with an injection port for injecting the addition-curing liquid silicone composition, and after the addition-curing liquid silicone composition is injected from the injection port and filled into the container of the first sealing structure, the injection port is sealed, forming the sealing portion.
  • the sealing part is preferably one in which a lid made of metal, glass, ceramic or resin is inserted, fitted or screwed onto the injection port into which the addition curing liquid silicone composition is injected, or the injection port itself is glued or welded (thermal welded) to seal the injection port.
  • the material of the lid part may be the same as that of the first sealing structure, and examples of the metal include aluminum, iron, stainless steel, etc., examples of the ceramic include alumina, etc., and examples of the resin include synthetic resins such as polyethylene, polypropylene, polyethylene terephthalate and polyvinyl chloride.
  • the first sealing structure may be a conventional container for storing an addition-curable liquid silicone composition.
  • the second sealing structure is a film that covers at least the entire sealing portion of the first sealing structure or the entire first sealing structure to further seal the sealing portion.
  • covering at least the entire sealing portion of the first sealing structure refers to a packaging form in which the second sealing structure covers the entire sealing portion of the first sealing structure to further seal it and may also cover the surrounding area.
  • the second sealing structure is preferably made of a resin film, and is preferably a laminated film of a resin layer and a metal layer, or a laminated film of a metal foil and a metal layer.
  • a laminated film of a resin layer (film) and a metal layer (foil) is preferred in order to achieve both strength, flexibility, and low permeability of the film, and it is particularly preferable that the metal layer (foil) of the laminated film be the outer surface of the second sealing structure.
  • the resin constituting the film, which is the second sealing structure is preferably a synthetic resin such as polyethylene, polypropylene, polyethylene terephthalate, or polyvinyl chloride.
  • the metal constituting the metal layer or metal foil is preferably aluminum.
  • the second sealing structure only needs to have a thickness that ensures the strength required for the second sealing structure and suppresses the transmission of air (i.e. oxygen and moisture) as much as possible.
  • the thickness is preferably 10 to 1,000 ⁇ m.
  • the thickness of the base resin layer or metal foil is preferably 10 to 1,000 ⁇ m, and the thickness of the laminated metal layer is preferably 5 to 50 ⁇ m.
  • Methods of further sealing with the second sealing structure include adhering a film-shaped second sealing structure to the outer periphery of the sealing portion of the first sealing structure with an adhesive or heat fusion, or placing the entire first sealing structure inside the bag-shaped second sealing structure and then sealing the opening of the second sealing structure by heat fusion or the like. That is, it is preferable that the second sealing structure covers at least the entire sealing portion of the first sealing structure, and is heat fused or adhered to the first sealing structure on the outer periphery of the sealing portion to further seal the sealing portion. Alternatively, it is preferable that the second sealing structure covers the entire first sealing structure, and the second sealing structure itself is sealed by heat fusion or adhesion to further seal the sealing portion.
  • the addition-curing liquid silicone composition is doubly sealed within the first sealing structure, and a member having the function of consuming and removing oxygen and moisture is attached between the first sealing structure and the second sealing structure.
  • the member having the function of consuming and removing oxygen and moisture is one that chemically reacts with oxygen and moisture in the space in which the member exists and absorbs them. This reduces the oxygen and moisture in the space (gap) between the first sealing structure and the second sealing structure, thereby preventing oxygen and moisture from entering the first sealing structure.
  • a gap is provided between the first sealing structure and the second sealing structure, and a member having a function of consuming and removing oxygen and moisture is attached to the gap, and in this case, it is more preferable that the member having a function of consuming and removing oxygen and moisture is disposed on the sealing portion of the first sealing structure. Also, the member having a function of consuming and removing oxygen and moisture may be fixed onto the sealing portion of the first sealing structure.
  • the function of the member having the function of consuming and removing oxygen and moisture is to absorb the oxygen and moisture by chemically reacting with the oxygen and moisture in the space in which the member is present. That is, in order to efficiently absorb oxygen and moisture in the gap between the first sealing structure and the second sealing structure, from the standpoint of cost and performance, it is preferable that the member having the function of consuming and removing oxygen and moisture is a member made of a so-called irreversible dehydrating and deoxidizing agent, such as one that uses a reaction in which metallic iron powder is oxidized by oxygen and moisture to become ferrous oxide or ferric oxide, or one that uses an exothermic reaction of calcium oxide with oxygen or a reaction with water to produce calcium hydroxide. It is also possible to absorb oxygen and moisture with separate members that are made of a combination of a dehydrating agent and a deoxidizing agent.
  • dehydrating and oxygen scavenging agents include RP System series products such as RP System RP-1AN, RP-3AN, RP-5AN, and RP-10AN (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
  • Combinations of dehydrating and oxygen scavenging agents include the Ageless Dry ADN series (ADN-5, etc.) (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a dehydrating agent (desiccant), and Ageless (Type S, etc.) (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a self-reacting iron-based oxygen scavenger.
  • the components capable of consuming and removing oxygen and moisture may be packaged so as not to inhibit the functions of these dehydrating and oxygen scavenging agents, or the functions of the dehydrating and oxygen scavenging agents.
  • the amount of the component having the function of consuming and removing oxygen and moisture i.e., the amount of dehydrating and deoxidizing agent, or the amount of dehydrating and deoxidizing agent in a combination of a dehydrating and deoxidizing agent, may be any amount necessary to efficiently absorb oxygen and moisture in the gap between the first sealing structure and the second sealing structure, and may be set appropriately.
  • a sealing portion is formed by sealing the opening of the first sealing structure during storage, and is further sealed by the second sealing structure, suppressing the inflow of air (i.e., oxygen and moisture) into the sealing portion.
  • air i.e., oxygen and moisture
  • oxygen and moisture in the narrow space (gap) between the sealing portion and the second sealing structure are removed by a member having the function of consuming and removing oxygen and moisture, which is attached between the first sealing structure and the second sealing structure, and thus the inflow of oxygen and moisture into the sealing portion is further suppressed, thereby further improving the storage and preservation properties of the aerobically curing addition-curing liquid silicone composition and increasing the flexibility of transportation.
  • the present invention will now be described in more detail with reference to the drawings.
  • the can in the present invention is a metal airtight container (tank) used for storing and transporting the addition-curable liquid silicone composition.
  • FIG. 1(a) The structure of a can, which is a first embodiment of a container for storing an addition-curable liquid silicone composition according to the present invention, is shown in Figure 1.
  • Figure 1(a) is a structural view of the entire container, and
  • Figure 1(b) is a cross-sectional view of the main part of this embodiment.
  • FIG. 1B shows a cross-sectional configuration of a portion surrounded by a dotted line in FIG.
  • An opening 11h is provided on the top surface of the main container 11a, surrounded by a dotted line, as an injection port through which the addition-curable liquid silicone composition is injected. After the addition-curable liquid silicone composition is injected, the opening 11h is sealed by inserting, fitting or screwing the lid 11b (sealing portion).
  • the main container 11a and the lid 11b constitute the first sealing structure described above.
  • the main container 11a and the lid 11b are preferably made of a metal such as aluminum, iron, or stainless steel.
  • the sealing film 12 is a sheet that covers the entire portion of the opening 11h (i.e., the injection port through which the addition-curing liquid silicone composition is injected) of the main container 11a sealed with the lid portion 11b (the sealing portion of the first sealing structure) as the second sealing structure described above, and further seals the sealing portion.
  • the sealing portion 12 is a film made of a synthetic resin such as polyethylene, or a laminated film in which a synthetic resin film such as polyethylene is laminated with a metal film or metal film such as aluminum.
  • the member 13 is a member that has the function of consuming and removing oxygen and moisture as described above, and is preferably attached to the gap between the portion where the opening 11h of the main container 11a is sealed with the lid portion 11b (the sealing portion of the first sealing structure) and the sealing film 12, and more preferably is fixed to the upper surface of the lid portion 11b.
  • the opening 11h of the main container 11a is sealed with the lid 11b to form a sealed portion, which is further sealed with the sealing film 12 to prevent the inflow of air (i.e., oxygen and moisture) into the sealed portion.
  • the member 13 attached between the lid 11b and the sealing film 12 removes oxygen and moisture in the narrow space (gap) between the sealing portion and the sealing film 12, further preventing the inflow of oxygen and moisture into the sealed portion, thereby further improving the preservability and storage properties of the aerobic curing addition-curing liquid silicone composition and increasing the flexibility of transportation.
  • the addition-curing liquid silicone composition when used, the addition-curing liquid silicone composition can be easily taken out by opening the lid 11b after removing the sealing film 12 and member 13 from the can 10, and the addition-curing liquid silicone composition can also be temporarily sealed by closing the lid 11b.
  • the cartridge in the present invention is also called a sealant cartridge, and is used for sealing and other construction work by storing an addition-curing liquid silicone composition sealed inside and attaching it to a cartridge gun (caulking gun) and discharging the addition-curing liquid silicone composition from a nozzle provided at the tip of the cartridge body container.
  • FIG. 2 is a schematic cross-sectional view of a cartridge which is a second embodiment of a container for storing an addition-curable liquid silicone composition according to the present invention.
  • the cartridge 20, which is a container for storing the addition-curable liquid silicone composition of the present invention includes a main container 21a filled with the addition-curable liquid silicone composition, a nozzle portion 21n, a plunger 21b, a sealing film 22 which is the second sealing structure described above, and a member 23 which is a member having the function of consuming and removing oxygen and moisture described above.
  • the main container 21a, the nozzle portion 21n, and the plunger 21b constitute the first sealing structure described above.
  • the main container 21a is a cylindrical container, one end of which is provided with a nozzle portion 21n capable of ejecting the addition-curing liquid silicone composition 1, and the other end is an opening that opens to the outside and serves as an injection port through which the addition-curing liquid silicone composition 1 can be injected.
  • This injection port is sealed by a plunger 21b provided inside it after the addition-curing liquid silicone composition 1 is injected (sealing portion).
  • the nozzle portion 21n provided at the tip of the main container 21a is a container that is integrated with the main container 21a when the cartridge 20 is stored, and when a part of it is cut with a knife or the like when the cartridge 20 is in use, a discharge hole is formed, and the addition-curing liquid silicone composition 1 filled in the main container 21a can be discharged to the outside from the discharge hole formed in the nozzle portion.
  • the plunger 21b inserted into the end of the main container 21a is provided so as to be able to slide along the inner surface of the main container 21a. With at least a portion of its outer periphery in contact with the inner periphery of the main container 21a, the plunger 21b moves along the inner surface of the main container 21a toward the nozzle portion 21n at the tip due to the pressing force from the cartridge gun (caulking gun), and as a result, the addition-curing liquid silicone composition 1 in the main container 21a is pressed by the plunger 21b and discharged to the outside through the discharge port of the nozzle portion 21n.
  • the main container 21a, the nozzle portion 21n, and the plunger 21b are preferably made of a synthetic resin such as polyethylene.
  • the main container 21a may also be made of a metal such as aluminum.
  • the sealing film 22 is a sheet-like material that covers the entire portion of the opening of the main container 21a (i.e., the injection port through which the addition-curing liquid silicone composition 1 is injected) sealed with the plunger 21b (the sealing portion of the first sealing structure) as the above-mentioned second sealing structure, and further seals the sealing portion.
  • the sealing portion 22 is a film made of a synthetic resin such as polyethylene, or a laminated film in which a synthetic resin film such as polyethylene is laminated with a metal film or metal film such as aluminum.
  • the member 23 is a member that has the function of consuming and removing oxygen and moisture as described above, and is preferably attached to the gap between the portion where the opening of the main container 21a is sealed with the plunger 21b (the sealing portion of the first sealing structure) and the sealing film 22, and more preferably is fixed to the upper surface of the plunger 21b.
  • the opening of the main container 21a is sealed by the plunger 21b during storage, and is further sealed by the sealing film 22 to prevent the inflow of air (i.e., oxygen and moisture) into the sealing part.
  • the sealing film 22 and member 23 are removed from the cartridge 20, and then the cartridge gun is attached to easily apply the addition-curing liquid silicone composition.
  • the package in the present invention is a packaging container in which a first sealing structure, which is a container such as a can, cartridge, or bag, is entirely covered and sealed with a film-like second sealing structure.
  • a first sealing structure which is a container such as a can, cartridge, or bag
  • Figure 3 shows the configuration of a package (1) which is a third embodiment of a container for storing an addition-curing liquid silicone composition according to the present invention.
  • Figure 3(a) is a diagram of the configuration before sealing with the second sealing structure
  • Figure 3(b) is a diagram of the configuration after sealing with the second sealing structure.
  • the package 30, which is a container for storing the addition-curing liquid silicone composition of the present invention, includes the main container 31, which is the first sealing structure described above, filled with the addition-curing liquid silicone composition 1, the sealing film 32, which is the second sealing structure described above, covering the entire main container 31 and member 33, and member 33, which has the function of consuming and removing oxygen and moisture, described above.
  • the main container 31 is a cylindrical container filled with the addition-curing liquid silicone composition 1, and has a sealing portion (not shown) formed by sealing the injection port through which the addition-curing liquid silicone composition 1 is injected.
  • the main container 31 is, for example, composed of the main container 21a, nozzle portion 21n, and plunger 21b in the cartridge 20 described above.
  • the sealing film 32 covers and seals the entire main container 31 and the member 33, and is preferably made of a film made of a synthetic resin such as polyethylene, or a laminated film in which a synthetic resin film such as polyethylene is laminated with a metal film such as aluminum, or a metal film.
  • the member 33 is a member that has the function of consuming and removing oxygen and moisture as described above, and is preferably fixed to the upper surface of the main container 31 where the sealing portion is located.
  • the package 30 can be manufactured by first storing the main container 31 filled with the addition-curing liquid silicone composition 1 and the member 33 placed on the top surface of the main container 31 in a bag-shaped sealing film 32a with an opening (Fig. 3(a)), and then gluing or heat-sealing the entire circumference of the sealing film 32a near the bag opening to form the bag opening into a sealing portion 32s (Fig. 3(b)). At this time, it is preferable to degas the inside of the sealing film 32a and then gluing or heat-sealing it so that the sealing film 32 hermetically seals the main container 31 and the member 33.
  • the sealing film 32a may be a so-called pouch container in which two sheet-like films are joined together and three sides are glued or heat-sealed.
  • the opening of the main container 31 is sealed to form a sealed portion during storage, which is further sealed by the sealing film 32 to prevent the inflow of air (i.e., oxygen and moisture) into the sealed portion.
  • the member 33 which is attached between the main container 31 and the sealing film 32 and has the function of consuming and removing oxygen and moisture, removes oxygen and moisture in the space (gap) between the sealing portion and the sealing film 32, further preventing the inflow of oxygen and moisture into the sealed portion, thereby further improving the preservability and storage properties of the aerobic curing addition curing liquid silicone composition 1 and increasing the flexibility of transportation.
  • the sealing film 32 is torn to open it, and the sealing film 32 and member 33 are removed, after which the main container 31 can be used for a specified purpose.
  • FIG. 4 shows the configuration of a package (2), which is a fourth embodiment of a container for storing an addition-curing liquid silicone composition according to the present invention.
  • the package 40 which is a storage container for the addition-curing liquid silicone composition of the present invention, includes a main container 41 made of a film, which is the first sealing structure described above, filled with the addition-curing liquid silicone composition 1, a sealing film 42, which is the second sealing structure described above, that covers the entire main container 41 and member 43, and a member 43, which has the function of consuming and removing oxygen and moisture, as described above.
  • the main container 41 is a packaging container made of a film material filled with the addition-curing liquid silicone composition 1, and is preferably made of a film made of a synthetic resin such as polyethylene, or a laminated film in which a synthetic resin film such as polyethylene is laminated with a metal film or metal film such as aluminum.
  • the main container 41 is initially a bag-shaped container, and has a sealing portion 41s in which the injection port (the entire circumference of the bag opening) through which the addition-curing liquid silicone composition 1 is injected is sealed by adhesion or heat fusion.
  • the main container 41 may also be a so-called pouch container in which two sheet-like films are joined together and the four sides are adhered or heat fused.
  • the sealing film 42 covers and seals the entire main container 41 and the member 43, and is preferably made of a film made of a synthetic resin such as polyethylene, or a laminated film in which a synthetic resin film such as polyethylene is laminated with a metal film such as aluminum, or a metal film.
  • the member 43 is a member that has the function of consuming and removing oxygen and moisture as described above, and is preferably fixed near the sealing portion 41s of the main container 41.
  • the package 40 can be manufactured by first storing the main container 41 filled with the addition-curing liquid silicone composition 1 and the member 43 arranged near the sealing portion 41s of the main container 41 in a bag-shaped sealing film having an opening, and then gluing or heat-sealing the entire circumference near the bag opening of the bag-shaped sealing film to form the bag opening into the sealing portion 42s. In this case, it is preferable to degas the inside of the bag-shaped sealing film and then gluing or heat-sealing the sealing film 42 so that the main container 41 and the member 43 are hermetically sealed.
  • the bag-shaped sealing film may be a so-called pouch container in which two sheet-like films are joined together and three sides are glued or heat-sealed.
  • the opening of the main container 41 is sealed to form a sealed portion 41s during storage, which is further sealed by the sealing film 42 to prevent the inflow of air (i.e., oxygen and moisture) into the sealed portion.
  • the member 43 which is attached between the main container 41 and the sealing film 42 and has the function of consuming and removing oxygen and moisture, removes oxygen and moisture from the space (gap) between the sealing portion 41s and the sealing film 42, further preventing the inflow of oxygen and moisture into the sealing portion 41s. This further improves the preservability and storage properties of the aerobic curing addition-curing liquid silicone composition 1, and increases the flexibility of transportation.
  • the sealing film 42 is torn to open it, and the sealing film 42 and member 43 are removed, after which the main container 41 can be used for a specified purpose.
  • addition-curable liquid silicone composition (addition-curable liquid silicone rubber composition or addition-curable liquid silicone gel composition) to be preserved in the present invention is preferably a composition containing the below-described components (A) to (C), and, if necessary, other components.
  • the alkenyl-containing diorganopolysiloxane of component (A) is a linear or branched diorganopolysiloxane having at least one, and preferably two or more, alkenyl groups per molecule, and acts as the main agent (base polymer) of the addition-curable liquid silicone composition that is the subject of the preservation of the present invention (hereinafter also referred to as the composition of the present invention).
  • the main chain portion is basically composed of repeating diorganosiloxane units, and is generally a linear diorganopolysiloxane in which both molecular chain terminals are blocked with triorganosiloxy groups, but this may also be a branched one that contains a branched structure as part of the siloxane structure that makes up the molecular chain.
  • the alkenyl-containing diorganopolysiloxane of component (A) contains at least one alkenyl group (usually 1 to 50), preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 or 2 alkenyl groups per molecule.
  • alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, and cyclohexenyl groups, which usually have about 2 to 8 carbon atoms.
  • the alkenyl group may be bonded to a silicon atom at the end of the molecular chain or to a silicon atom at a non-terminal end (in the middle of the molecular chain), and it is preferable that the alkenyl group contains an alkenyl group bonded to a silicon atom at at least (both) ends of the molecular chain. In this case, the alkenyl group may be present only at both ends of the molecular chain, or may be present at both ends of the molecular chain and non-terminal ends (in the middle of the molecular chain).
  • alkenyl-containing diorganopolysiloxanes examples include linear diorganopolysiloxanes represented by the following general formula (1).
  • R1 is independently an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bonds
  • X is an alkenyl group, at least one of which is contained in the molecule
  • n is an integer of 0 or more
  • m is an integer of 0 or more
  • a is an integer of 0 to 3 independently for each silicon atom to which it is bonded.
  • examples of the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond for R 1 include those having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and biphenylyl; and aralkyl groups such as benzyl, phenylethyl, phenylpropyl, and methylbenzyl.
  • halogen atoms such as fluorine, chlorine or bromine
  • a cyano group for example, a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a chlorophenyl group, a fluorophenyl group, a cyanoethyl group, a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like, are preferred, including unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, a cyanoethyl group, and the
  • examples of the alkenyl group for X include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, and cyclohexenyl groups, each of which has about 2 to 8 carbon atoms. Of these, lower alkenyl groups such as vinyl and allyl are preferred.
  • n is an integer of 0 or more, preferably an integer of 10 to 2,000, more preferably an integer of 50 to 1,200
  • m is an integer of 0 or more, preferably an integer of 0 to 40, more preferably an integer of 0 to 20.
  • n and m are preferably integers that satisfy 10 ⁇ n+m ⁇ 2,000, more preferably 50 ⁇ n+m ⁇ 1,200 and 0 ⁇ m/(n+m) ⁇ 0.2.
  • the units in parentheses enclosed by n and m may be arranged randomly.
  • a is an integer from 0 to 3, preferably an integer from 1 to 3, for each silicon atom to be bonded.
  • alkenyl group-containing diorganopolysiloxanes preferably have a viscosity at 23°C of 10 to 1,000,000 mPa ⁇ s, and more preferably 100 to 500,000 mPa ⁇ s.
  • the number of repetitions (or degree of polymerization) of diorganosiloxane units in a molecule can be determined as the polystyrene-equivalent number average molecular weight (or number average degree of polymerization) in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent.
  • Viscosity can be measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.) at 23°C.
  • the alkenyl-containing diorganopolysiloxane of component (A) may be used alone or in combination of two or more types.
  • the organohydrogenpolysiloxane of component (B) is an organohydrogenpolysiloxane having a linear, cyclic, branched, or three-dimensional network structure that has at least two hydrogen atoms bonded to silicon atoms (SiH groups) in each molecule, and functions as a curing agent (crosslinking agent) for the addition-curable liquid silicone composition that is the subject of the preservation of the present invention.
  • the organohydrogenpolysiloxane of component (B) acts as a curing agent (crosslinking agent) for the composition to be preserved of the present invention, and contains at least 2 (usually 2 to 200), and preferably about 3 to 100 hydrogen atoms bonded to silicon atoms (i.e., SiH groups) in one molecule, and may have a linear, branched, cyclic, or three-dimensional network structure (resin structure).
  • organohydrogenpolysiloxanes examples include those represented by the following average composition formula (2).
  • R2 is independently an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bonds
  • b and c are numbers that satisfy 0.001 ⁇ b ⁇ 1.2, 0.8 ⁇ c ⁇ 2, and 0.8 ⁇ b+c ⁇ 3, and preferably 0.05 ⁇ b ⁇ 1, 1.5 ⁇ c ⁇ 2, and 1.8 ⁇ b+c ⁇ 2.7.
  • examples of the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bonds for R2 include the same as those exemplified for R1 in general formula (1) above, such as groups having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and particularly preferably a lower alkyl group having 1 to 3 carbon atoms, such as a methyl group, a phenyl group, or a 3,3,3-trifluoropropyl group.
  • the (B) component is preferably one that is liquid at room temperature and has 2 to 300 silicon atoms in one molecule, particularly 2 to 150, and especially 2 to 100.
  • the hydrogen atoms bonded to the silicon atoms may be located at either the ends of the molecular chain, or in the middle of the molecular chain (non-terminal), or may be located at both.
  • organohydrogenpolysiloxanes examples include methylhydrogencyclosiloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, and 1,3,5,7,9-pentamethylpentacyclosiloxane; tris(dimethylhydrogensiloxy)methylsilane; tris(dimethylhydrogensiloxy)phenylsilane; methylhydrogenpolysiloxanes capped with trimethylsiloxy groups at both molecular chain terminals; dimethylsiloxane-methylhydrogensiloxane copolymers capped with trimethylsiloxy groups at both molecular chain terminals; diphenylsiloxane-methylhydrogensiloxane copolymers capped with trimethylsiloxy groups at both molecular chain terminals; and methylhydr
  • the organohydrogenpolysiloxane used in the addition-curable liquid silicone composition to be preserved in the present invention can be obtained by known methods, for example, by cohydrolyzing at least one chlorosilane selected from the general formulas R2SiHCl2 and R22SiHCl (wherein R2 is the same as above), or by combining and cohydrolyzing said chlorosilane with at least one chlorosilane selected from the general formulas R23SiCl and R22SiCl2 (wherein R2 is the same as above).
  • the organohydrogenpolysiloxane may also be one obtained by equilibrating the polysiloxane obtained by such cohydrolysis.
  • the amount of organohydrogenpolysiloxane (B) blended is desirably such that the number of hydrogen atoms bonded to silicon atoms (i.e., SiH groups) in the organohydrogenpolysiloxane (B) is 0.5 to 4 moles, preferably 0.8 to 2.5 moles, per mole of alkenyl groups in the alkenyl-containing diorganopolysiloxane (A).
  • the organohydrogenpolysiloxane of component (B) may be used alone or in combination of two or more types.
  • the addition-curable liquid silicone composition to be preserved in the present invention is characterized by the incorporation of an aerobic (aerobic reactive) platinum catalyst (a platinum catalyst that is inactive under closed conditions (low moisture and low oxygen conditions) that are cut off from contact with the atmosphere, and that is activated when exposed to the atmosphere) as the platinum catalyst of component (C) for promoting the hydrosilylation addition reaction between the alkenyl group in component (A) and the hydrogen atom (SiH group) bonded to a silicon atom in component (B).
  • an aerobic (aerobic reactive) platinum catalyst a platinum catalyst that is inactive under closed conditions (low moisture and low oxygen conditions) that are cut off from contact with the atmosphere, and that is activated when exposed to the atmosphere
  • platinum catalyst of component (C) for promoting the hydrosilylation addition reaction between the alkenyl group in component (A) and the hydrogen atom (SiH group) bonded to a silicon atom in component (B).
  • Specific examples of component (C) include all of the platinum catalyst mixtures contained
  • the platinum catalyst mixture used in component (C) is an aerobic catalyst consisting of a reaction mixture of a platinum-alkenyl group-containing organosiloxane complex and an organosilicon compound having at least one SiH group in the molecule in an amount such that the number of hydrogen atoms bonded to silicon atoms (SiH groups) is in molar excess (molar ratio of greater than 1) relative to the alkenyl groups in the platinum-alkenyl group-containing organosiloxane complex.
  • the platinum-alkenyl group-containing organosiloxane complex is preferably a complex of platinum, platinum chloride, chloroplatinic acid or chloroplatinate with a vinyl group-containing siloxane (for example, an organodisiloxane compound having two alkenyl groups in the molecule, such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane).
  • a vinyl group-containing siloxane for example, an organodisiloxane compound having two alkenyl groups in the molecule, such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.
  • the platinum-alkenyl group-containing organosiloxane complex is preferably used by dissolving it in a solvent such as toluene, lower alcohol, higher alcohol, or silicone.
  • a solvent such as toluene, lower alcohol, higher alcohol, or silicone.
  • the platinum atom content (content concentration) in the solution is preferably 0.05 to 5 mass%.
  • the organosilicon compound having at least one hydrogen atom (SiH group) bonded to a silicon atom can be an organohydrogensilane or an organohydrogensiloxane oligomer having at least one SiH group in the molecule (for example, 1 to 10, preferably 1 to 5). From the standpoint of ease of handling and safety, an organohydrogensiloxane oligomer is more preferred, and an organohydrogensiloxane oligomer having at least two hydrogen atoms (adjacent SiH groups) in the molecule, each of which is bonded to adjacent silicon atoms via an ether oxygen atom that forms a siloxane bond (Si-O-Si), is even more preferred.
  • the molecular structure of this organohydrogensiloxane oligomer may be linear or cyclic, and the number of silicon atoms in one molecule is preferably 2 to 40, more preferably 2 to 10, and even more preferably 2 to 5.
  • organohydrogensilane and organohydrogensiloxane oligomer used here may, for example, be trialkoxy(hydrogen)silane, alkyldialkoxy(hydrogen)silane, dialkylalkoxy(hydrogen)silane, 1,1,1,3,3-pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and 1,3,5,7,9-pentamethylcyclopentasiloxane, and one or more of these exemplary compounds may be used.
  • the above platinum catalyst mixture is a reaction mixture in which the alkenyl groups in the platinum-alkenyl group-containing organosiloxane complex react with the SiH groups derived from the above organosilicon compound, which is added in an excess molar amount relative to the alkenyl groups during preparation of the mixture (i.e., more than 1 mole per mole of the alkenyl groups, preferably 1.1 to 30 moles, more preferably 1.5 to 25 moles, and even more preferably about 5 to 25 moles) in an oxygen-free atmosphere, so that all of the alkenyl groups are converted to alkylene groups by a hydrosilylation addition reaction (the alkenyl groups have essentially disappeared), and excess SiH groups derived from the organosilicon compound remain in the mixture.
  • an excess molar amount relative to the alkenyl groups during preparation of the mixture i.e., more than 1 mole per mole of the alkenyl groups, preferably 1.1 to 30 moles, more preferably 1.5 to 25 moles,
  • the organosilicon compound having at least one hydrogen atom bonded to the silicon atom is an organohydrogensiloxane oligomer having at least two hydrogen atoms (hereinafter sometimes referred to as adjacent SiH groups) in the molecule bonded to adjacent silicon atoms (hereinafter sometimes referred to as adjacent silicon atoms) via ether oxygen atoms that form a siloxane bond (Si-O-Si) (for example, when the organosilicon compound is 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-pentamethylcyclopentasiloxane, etc.), In the case where the organohydrogensiloxane oligomer having at least two adjacent SiH groups and the platinum-alkenyl group-containing organo
  • the reaction mixture is preferably obtained by mixing the organohydrogensiloxane oligomer having at least two adjacent SiH groups and the platinum-alkenyl group-containing organosiloxane complex in a state in contact with moisture and/or oxygen in a blending ratio such that the SiH groups in the organohydrogensiloxane oligomer having at least two adjacent SiH groups are in molar excess relative to the alkenyl groups in the platinum-alkenyl group-containing organosiloxane complex.
  • an addition-curing liquid silicone composition that contains this mixture as a hydrosilylation addition reaction catalyst can achieve even greater long-term one-part storage stability under sealed conditions without losing its curability when in contact with moisture (humidity) and/or oxygen in the air.
  • the method for preparing the platinum catalyst mixture is characterized by mixing the platinum-alkenyl group-containing organosiloxane complex with an organosilicon compound having at least one hydrogen atom (SiH group) bonded to a silicon atom in the molecule in a ratio such that the SiH groups of the organosilicon compound are in molar excess relative to the alkenyl groups in the platinum-alkenyl group-containing organosiloxane complex in an oxygen-free atmosphere (for example, in an oxygen-free, low-moisture sealed environment that is isolated from contact with moisture (humidity) and oxygen) to obtain a reaction mixture.
  • an oxygen-free atmosphere for example, in an oxygen-free, low-moisture sealed environment that is isolated from contact with moisture (humidity) and oxygen
  • the blending ratio at which the SiH groups of the organosilicon compound are in excess of moles relative to the alkenyl groups in the platinum-alkenyl group-containing organosiloxane complex means that the blending amounts of the platinum-alkenyl group-containing organosiloxane complex and the organosilicon compound are such that the SiH groups in the organosilicon compound are greater than 1 mole per mole of alkenyl groups in the complex, preferably 1.1 to 30 moles, more preferably 1.5 to 25 moles, and even more preferably about 5 to 25 moles.
  • the mixing method is not particularly limited as long as it is a method that uniformly mixes the platinum-alkenyl group-containing organosiloxane complex and the organosilicon compound having at least one hydrogen atom bonded to a silicon atom (SiH group) in the molecule, but it is preferable to use a glass reactor such as a glass flask or a stainless steel reactor.
  • the atmosphere during mixing is preferably oxygen-free, and is preferably an inert gas atmosphere such as nitrogen or reduced pressure (vacuum). There is no need to heat the mixture, and room temperature (23°C ⁇ 15°C, the same applies below) can be used.
  • the mixing time i.e., reaction time
  • the organosilicon compound having at least one hydrogen atom bonded to a silicon atom in the platinum catalyst mixture is an organohydrogensiloxane oligomer having at least two hydrogen atoms in the molecule bonded to adjacent silicon atoms via ether oxygen atoms forming a siloxane bond (Si-O-Si) (for example, when the organosilicon compound is 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-pentamethylcyclopentasiloxane, etc.), it is preferable that the method further includes a step of mixing the reaction mixture obtained by mixing in the oxygen-free atmosphere while contacting it with moisture and/or oxygen.
  • the reaction mixture is brought into contact with moisture and/or oxygen by means of mixing in the atmosphere, and the mixing time in the atmosphere is preferably 0.5 to 100 hours, and more preferably 1 to 12 hours.
  • the platinum catalyst mixture is stored in a sealed container.
  • another method for preparing a platinum catalyst mixture is a method for preparing a platinum catalyst mixture by mixing a platinum-alkenyl group-containing organosiloxane complex with an organosilicon compound having at least one hydrogen atom (SiH group) bonded to a silicon atom in the molecule to obtain a reaction mixture, characterized in that the organosilicon compound having at least one hydrogen atom bonded to a silicon atom in the molecule is an organohydrogensiloxane oligomer having at least two hydrogen atoms (adjacent SiH groups) in the molecule bonded to adjacent silicon atoms via oxygen atoms that form siloxane bonds (Si-O-Si), and the platinum-alkenyl group-containing organosiloxane complex and the organosilicon compound having at least one hydrogen atom (SiH group) bonded to a silicon atom in the molecule are mixed in a state in contact with moisture and/or oxygen in a blending ratio such that the SiH groups
  • an addition-curing liquid silicone composition that contains this mixture as a hydrosilylation addition reaction catalyst can achieve even greater long-term one-part storage stability under sealed conditions without losing its curability when in contact with moisture (humidity) and/or oxygen in the air.
  • the platinum catalyst mixture obtained in the above manner has low catalytic activity as a hydrosilylation addition reaction catalyst in a sealed container that is protected from contact with oxygen and has a low moisture content, but when it comes into contact with moisture (humidity) and/or oxygen in the air, its catalytic activity becomes high.
  • this platinum catalyst mixture when added as a curing catalyst to a hydrosilylation addition reaction curing type curable liquid silicone composition, when the curable liquid silicone composition is stored in a sealed container that is protected from contact with oxygen and has a low moisture content, the composition can exhibit a sufficiently long-term one-part storage stability under refrigeration to room temperature, while when the sealed container is opened and the composition comes into contact with moisture (humidity) and/or oxygen in the air, the platinum catalyst mixture in the composition is activated at room temperature and becomes highly catalytically active, and in the curable liquid silicone composition, the crosslinking (curing) reaction by the hydrosilylation addition reaction proceeds quickly even without heating, and not only the surface exposed to air but also the deep parts are quickly cured, and the curable liquid silicone composition can be rubberized and gelled.
  • the amount of the platinum catalyst mixture in component (C) may be a so-called catalytic amount, but it is an amount that is 0.1 to 1,000 ppm, preferably 0.5 to 200 ppm, calculated as the mass of platinum atoms contained in component (C) relative to the total mass of components (A) and (B). If the amount of component (C) is less than the above range, the material will not cure sufficiently due to the influence of catalyst inhibition factors when used, and if it is more than the above range, the storage stability will be poor.
  • component (C) is a so-called catalytic amount
  • the excess molar amount of SiH groups remaining in component (C) is negligibly small and does not substantially affect the molar ratio of SiH groups in component (B) to the alkenyl groups in component (A) described above.
  • addition-curable liquid silicone composition that is the subject of preservation in the present invention can contain various optional components as described below, as necessary, to the extent that the performance of the addition-curable liquid silicone composition is not impaired.
  • the addition-curable liquid silicone composition to be preserved in the present invention can further contain, as an optional component, a dehydrating agent (D) to remove water from the composition, if necessary.
  • a dehydrating agent (D) to remove water from the composition, if necessary.
  • the platinum catalyst mixture of component (C) which is the core technology of this addition-curing liquid silicone composition, has the property that its catalytic activity is kept low in an oxygen-free, low-moisture environment where contact with moisture (humidity) and oxygen is blocked, and its catalytic function is activated by moisture and/or oxygen from the outside air (atmosphere) (aerobic reaction type).
  • the one-part shelf life of addition-curing liquid silicone compositions can be improved by reducing the amount of moisture in each component and in the mixed composition, and it is useful in ensuring the shelf life of one-part compositions to introduce a mechanism that consumes (dehydrates) moisture from the components and trace amounts of moisture that enter from outside the container within the composition when stored in a sealed container.
  • the compound that enables this dehydration may be either an inorganic compound or an organic compound, so long as it does not impair the functions of the above components (A), (B), and (C).
  • foaming may occur due to the by-product compound produced by the dehydration reaction, and many of them may also cause decomposition of the hydrogen siloxane in the composition or a decrease in the catalytic activity of the platinum catalyst mixture.
  • silyl ketenes including silyl ketene acetals
  • silyl enol esters and ⁇ -silyl esters are suitable as dehydrating agents for component (D), as they enable efficient dehydration within the system.
  • These compounds have a structure in which the by-products produced during dehydration do not impair the functions of components (A), (B), and (C) above, and are soluble in the addition-curable liquid silicone composition, making it possible to form a stable curable liquid silicone composition.
  • silyl ketenes including silyl ketene acetals
  • ⁇ -silyl esters undergo a dehydration reaction in a non-basic environment, so they do not cause decomposition of hydrogen siloxanes or a decrease in the catalytic activity of the platinum catalyst mixture.
  • Silyl ketenes (containing silyl ketene acetals) include 1-methoxy-2-methyl-1-(trimethylsiloxy)propene, dimethyl ketene trimethylsilyl acetal, and tert-butoxy-1-(trimethylsiloxy)propene.
  • ⁇ -silyl esters examples include ethyl 2-(trimethoxysilyl)propionate (ECMS) and octyl 2-(methyldimethoxysilyl)propionate (OCMS-2).
  • the dehydrating agent (D) may be added to each component in advance, may be added during the preparation of the composition, or may be added after the composition has been prepared.
  • the amount added is preferably 5% by mass or less, and more preferably 2% by mass or less, of the total composition.
  • a catalyst may also be added to promote the reaction between component (D) and water.
  • catalysts include titanate esters (tetra(isopropyl)titanate (TPT), tetrabutyltitanate (TBT), tetra(2-ethylhexyl)titanate (TOT), etc.), titanium chelate compounds (titanium diisopropoxybis(ethylacetoacetate), titanium tetraacetylacetonate, etc.), tin compounds (dibutyldimethoxytin, dibutyltin dilaurate, etc.).
  • the amount of catalyst added is preferably 2% by mass or less of the total composition, and more preferably 1% by mass or less.
  • the platinum catalyst mixture of component (C) which is the core technology of this addition-curing liquid silicone composition, has the property that its catalytic function is activated by moisture. For this reason, some of the platinum catalyst mixture of component (C) may be activated as an addition reaction catalyst due to moisture in each component, moisture mixed in during the process of preparing the composition or filling the container, and even moisture entering from outside the sealed container. This partially activated catalyst may significantly reduce the one-part shelf life of the composition, but such a decrease in one-part shelf life can be suppressed by supplementarily adding the addition reaction inhibitor of component (E).
  • Addition reaction inhibitors for component (E) include acetylene alcohols such as 1-ethynylcyclohexanol and 3-methyltridec-1-yn-3-ol (EMDC), and silanes and siloxane-modified acetylene alcohols such as dimethylbis(1,1-dimethyl-2-propynyloxy)silane (PLR-22) and 3-(trimethylsilyloxy)-3-methyl-1-butyne (PLR-31), tri(isopropyl)phosphite, tris(di-tert-butylphenyl)phosphite, triphenylphosphite, tris(2-ethyl)
  • suitable compounds include compounds selected from the group consisting of phosphorous acid compounds (particularly phosphorous acid esters) such as tris(isopropyl)phosphite and tris(di-tert-butylphenyl)phosphite, ethylenediamines such as
  • phosphorous acid compounds particularly the phosphorous acid esters tri(isopropyl)phosphite and tris(di-tert-butylphenyl)phosphite are preferred because they provide an addition-curable liquid silicone composition that has good one-liquid storage stability under airtightness.
  • the amount of the addition reaction inhibitor (E) added may be any amount depending on the performance of the respective addition reaction inhibitor, so long as it does not affect the curing properties of the addition-curable liquid silicone composition.
  • the amount added may be very small, less than 1 mole, and in particular about 0 to 0.75 moles, per mole of platinum atoms contained in the composition. If too much component (E) is added, the platinum catalyst mixture (C) activated by moisture during use will be deactivated, and there is a risk of reduced curing properties when exposed to the atmosphere.
  • the addition-curable liquid silicone composition to be preserved in the present invention may further contain an inorganic filler (F) as an optional component, as necessary, for adjusting the viscosity when uncured, improving the strength of the cured silicone rubber or cured silicone gel product after curing, and adjusting the appearance color.
  • an inorganic filler (F) as an optional component, as necessary, for adjusting the viscosity when uncured, improving the strength of the cured silicone rubber or cured silicone gel product after curing, and adjusting the appearance color.
  • the inorganic filler (F) that may be added include reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide; and non-reinforcing inorganic fillers such as calcium silicate, titanium dioxide, ferric oxide, and carbon black.
  • the amount of inorganic filler in component (F) is usually 200 parts by mass or less per 100 parts by mass of component (A). When component (F) is used, it is preferably 0.1 to 200 parts by mass, more preferably 0.5 to 50 parts by mass, per 100 parts by mass of component (A). If the amount of inorganic filler used is less than 0.1 part by mass, the effect of adding it may not be obtained, and if it exceeds 200 parts by mass, it may be difficult to mix it uniformly into a mixture.
  • the addition-curable liquid silicone composition to be preserved according to the present invention may further contain, as an optional component as necessary, a hydrolyzable organosilane compound (so-called carbon functional silane or silane coupling agent) such as an alkoxysilane containing a monovalent hydrocarbon group having a functional group containing a heteroatom selected from oxygen atoms, nitrogen atoms and sulfur atoms (epoxy groups, (meth)acryloxy groups, mercapto groups, etc.) and/or a partial hydrolysis condensate thereof as an adhesion-imparting agent for component (G) in order to improve the adhesion of the cured product to various substrates.
  • a hydrolyzable organosilane compound such as an alkoxysilane containing a monovalent hydrocarbon group having a functional group containing a heteroatom selected from oxygen atoms, nitrogen atoms and sulfur atoms (epoxy groups, (meth)acryloxy groups, mercapto groups, etc.
  • the amount is preferably 0.1 to 20 parts by mass, and more preferably about 0.2 to 10 parts by mass, per 100 parts by mass of the (A) component. If the amount of adhesive agent is less than 0.1 parts by mass, the desired adhesiveness will not be achieved sufficiently, and if it is more than 20 parts by mass, the viscosity of the material may decrease dramatically.
  • the addition-curable liquid silicone composition to be preserved in the present invention may further contain, as an optional component, a plasticizer (H) in order to adjust the viscosity of the composition and the hardness of the cured product, as necessary.
  • a plasticizer H
  • This may be so-called non-functional silicone oils, such as dimethylpolysiloxane (dimethylsilicone oil) capped at both molecular terminals with trimethylsilyl groups, dimethylsiloxane-diphenylsiloxane copolymer capped at both molecular terminals with trimethylsilyl groups, or dimethylsiloxane-methylphenylsiloxane copolymer (methylphenylsilicone oil) capped at both molecular terminals with trimethylsilyl groups, which do not contain functional groups in the molecule that participate in hydrosilylation addition reactions, such as alkenyl groups or hydrosilyl groups (SiH groups).
  • the amount is preferably 0.1 to 50 parts by mass, and more preferably about 0.5 to 20 parts by mass, per 100 parts by mass of component (A). If the amount of non-functional silicone oil (plasticizer) is less than 0.1 parts by mass, the plasticization intended by its addition may not be achieved, and if it is more than 50 parts by mass, the plasticizer may separate and bleed out of the material after curing.
  • the addition-curing liquid silicone composition to be preserved in the present invention may contain, in addition to the optional components (D) dehydrating agent, (E) addition reaction regulator, (F) inorganic filler, (G) adhesion promoter, and (H) plasticizer described above, additives such as pigment pastes using the same components as the non-functional silicone oil used as the plasticizer as a binder, or reinforcing silicone resins, as other optional components, if necessary.
  • the container for storing the addition-curable liquid silicone composition of the present invention may be produced by the following procedure.
  • the prepared addition-curable liquid silicone composition is poured into a container constituting the first sealing structure through its injection port under the same environment as during preparation (room temperature, in an environment of low oxygen concentration (substantially oxygen-free) and low moisture content where contact with moisture (humidity) and oxygen is blocked), and a lid made of metal, glass, ceramic, or resin is inserted, fitted, or screwed into the injection port, or the injection port itself is glued or welded (thermal welded) to seal the injection port, thereby forming a first sealing structure.
  • a member having a function of consuming and removing oxygen and moisture (a dehydrating and oxygen scavenging agent, or a combination of a dehydrating and oxygen scavenging agent) is attached to the sealing portion of the first sealing structure or in the vicinity thereof.
  • the second sealing structure covers at least the entire sealing portion of the first sealing structure, or covers the entire first sealing structure, and further seals the sealing portion and the member having the function of consuming and removing oxygen and moisture.
  • the second sealing structure in a film shape is fixed to the outer periphery of the sealing portion of the first sealing structure by adhesive or heat fusion, thereby "covering at least the entire sealing portion of the first sealing structure.”
  • the entire first sealing structure is placed inside the bag-shaped second sealing structure, and the opening of the second sealing structure is sealed by heat fusion or adhesion, thereby "covering the entire first sealing structure.” In this manner, a container for storing the addition-curable liquid silicone composition of the present invention is obtained.
  • the method for curing the addition-curable liquid silicone composition to be preserved in the present invention is characterized by the steps of removing the addition-curable liquid silicone composition from the storage container described above and exposing it to the atmosphere at room temperature to cure it.
  • addition-curing liquid silicone composition When the addition-curing liquid silicone composition is exposed to the atmosphere, moisture (humidity) and/or oxygen from the atmosphere come into contact with the platinum catalyst mixture of component (C) in the composition, activating the catalytic function of the platinum catalyst mixture, and curing of the addition-curing liquid silicone composition begins even at room temperature. At this time, not only the surface of the composition that comes into contact with the air but also the deeper parts quickly cure, producing a cured silicone rubber or cured silicone gel.
  • the silicone rubber and silicone gel obtained as the cured product of the addition-curing liquid silicone composition in this way have excellent heat resistance and electrical insulation properties, and can be used in automotive parts, aircraft, home appliances, etc.
  • the viscosity is measured using a rotational viscometer at 23°C, and the degree of polymerization is the number-average degree of polymerization in terms of polystyrene in GPC analysis using toluene as the developing solvent.
  • Me represents a methyl group
  • Vi represents a vinyl group.
  • Room temperature means 23°C.
  • the oxygen concentration in the "atmosphere” is 21% by volume, and the humidity is 50% RH.
  • an aerobic platinum catalyst mixture (C-1) was prepared as follows. (Preparation instructions) Under a nitrogen atmosphere at room temperature (23°C), a toluene solution of chloroplatinic acid-1,3-divinyltetramethyldisiloxane complex (C-a) as a platinum-alkenyl group-containing organosiloxane complex (platinum atom content 0.5 mass%) and 1,1,3,3-tetramethyldisiloxane (C-b) as an organohydrogenpolysiloxane were uniformly mixed and reacted in a 25 g glass bottle in the blending ratio shown in Table 1 below over 12 hours, and then the bottle was sealed. Furthermore, the lid of the glass bottle was opened in the atmosphere at room temperature (23°C), and the mixture was uniformly mixed while being in contact with the atmosphere for another 2 hours, and then the bottle was sealed, thereby preparing
  • addition-curable liquid silicone compositions (S-1) to (S-4) were prepared as follows:
  • compositions were prepared by uniformly mixing the components in the amounts shown in Table 2 below in a glass bottle under a nitrogen atmosphere at room temperature (23°C) and sealing the bottle in order to prepare each composition.
  • Table 2 the molar ratio of SiH groups in component (B) to vinyl groups in component (A) for compositions (S-1) to (S-4) was 2.2 for all of them.
  • the ingredients were added in the following order while mixing: (A) alkenyl-containing diorganopolysiloxane, (B) organohydrogenpolysiloxane, (D) dehydrating agent, (E) addition reaction inhibitor, and (C) aerobic platinum catalyst mixture.
  • (B) Organohydrogenpolysiloxane: (B-1) Linear organohydrogenpolysiloxane represented by the following average formula: (Me) 3 SiO-(Si(Me) 2 O) 63 -(Si(H)(Me)O) 20 -Si(Me) 3 (B-2) Linear organohydrogenpolysiloxane represented by the following average formula: H(Me) 2SiO- (Si(Me) 2O ) 18 -SiH(Me) 2
  • ECMS Ethyl 2-(trimethylsilyl)propionate
  • TPT tetra(isopropyl)titanate
  • Zr(O--Pr) 4 tetraisopropoxyzirconium(IV)
  • the prepared curable liquid silicone compositions were evaluated for their one-part storage stability under a closed container, their curability after storage in the open air at room temperature (room temperature curability), and hardness of the cured product, as described below.
  • the one-part storage stability under a tight seal was evaluated by filling a curable liquid silicone composition into a glass bottle under a nitrogen atmosphere and sealing it (i.e., filling 10 g of the composition shown in Table 2 into a glass bottle (external dimensions: diameter 35 mm, height 65 mm) in nitrogen, and then fitting (pressing) a lid (a hat-shaped polyethylene inner stopper in which the part in contact with the glass bottle's injection port is made, and a metal cap in which the part to be pressed is made (polyethylene inner stopper + metal cap)) onto the injection port (opening) of the glass bottle to form a sealed container (the first sealed structure in the present invention, hereinafter referred to as the glass bottle)), and leaving the glass bottle in the air/room temperature to observe the thick
  • the thickening and gelling behavior of the curable liquid silicone composition was evaluated by observing the degree to which the composition in the glass bottle flows when the glass bottle is tilted (fluidity), and a state in which the fluidity became worse than it was immediately after sealing was determined to be one in which the curable liquid silicone composition had thickened or gelled.
  • the sealed glass bottle containing the curable liquid silicone composition was left in the air/at room temperature and then observed for five minutes, and thereafter observed every day to confirm the time (number of days) until the curable liquid silicone composition thickened or gelled.
  • the room temperature curability was evaluated by taking the curable liquid silicone composition stored in a sealed glass bottle for one day as described above, placing it in a separate container (depth 4 mm) under a nitrogen atmosphere, exposing it to the atmosphere/room temperature, and measuring the time it took to cure into a rubber or gel state as the curing time. At this time, a needle was inserted into the container to check the state of cure in the deeper part.
  • the hardness of the cured product was measured by casting the curable liquid silicone rubber composition immediately after preparation as obtained above into a glass petri dish and exposing it to an air/room temperature environment for 24 hours.
  • Example 1 The prepared glass bottle was placed in a bag made of polyethylene film (polyethylene bag, thickness 110 ⁇ m) and one dehydrating and oxygen scavenger (RP System RP-1AN, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was placed near the lid of the glass bottle as a member having the function of consuming and removing oxygen and moisture.
  • the opening of the polyethylene bag was then sealed by heat fusion to hermetically seal the glass bottle and the dehydrating and oxygen scavenger, thereby preparing a storage container.
  • This sealed polyethylene bag is the second sealing structure. Note that this storage container corresponds to the package 30 shown in Figure 3, with the glass bottle being the main container 31, the polyethylene bag being the sealing film 32, and the dehydrating and oxygen scavenger being member 33.
  • Example 2 A storage container was produced in the same manner as in Example 1, except that a bag (aluminum-laminated polyethylene bag, thickness 100 ⁇ m) made by laminating aluminum foil (thickness 10 ⁇ m) to the outer surface side of a polyethylene film (thickness 90 ⁇ m) was used instead of the polyethylene bag in Example 1.
  • This storage container corresponds to the package 30 shown in Fig. 3, with the glass bottle being the main container 31, the aluminum-laminated polyethylene bag being the sealing film 32, and the dehydrating and oxygen absorbing agent being the member 33.
  • Example 2 A storage container was produced in the same manner as in Example 1, except that no dehydrating or oxygen scavenging agent was added.
  • Example 3 A storage container was prepared in the same manner as in Example 1, except that a single dehydrating agent having only a dehydrating function (Ageless Dry ADN-5 (manufactured by Mitsubishi Gas Chemical Co., Ltd.)) was used instead of the dehydrating and oxygen scavenging agent used in Example 1.
  • a single dehydrating agent having only a dehydrating function (Ageless Dry ADN-5 (manufactured by Mitsubishi Gas Chemical Co., Ltd.)) was used instead of the dehydrating and oxygen scavenging agent used in Example 1.
  • Example 4 A storage container was prepared in the same manner as in Example 1, except that one oxygen absorber (Ageless FJ (manufactured by Mitsubishi Gas Chemical Co., Ltd.)) having only oxygen absorbing function was used instead of the dehydrating and oxygen absorbing agent in Example 1.
  • one oxygen absorber Ageless FJ (manufactured by Mitsubishi Gas Chemical Co., Ltd.) having only oxygen absorbing function was used instead of the dehydrating and oxygen absorbing agent in Example 1.
  • Example 5 A storage container was produced in the same manner as in Example 1 except that no dehydrating or oxygen scavenging agent was added in Example 2.
  • a first sealing structure in the present invention 250 g of the composition shown in Table 2 was filled in a metal (aluminum) cartridge body container (external dimensions: diameter 47 mm, height 215 mm) in nitrogen, and then a lid (plunger (made of aluminum, outer diameter 46 mm)) was inserted into the injection port (opening, inner diameter 46 mm) of the cartridge to seal the container (hereinafter referred to as a cartridge container).
  • a storage container was prepared using the combination shown in Table 3, and the storage stability of the filled composition was evaluated.
  • Example 3 A piece of dehydrating and oxygen absorbing agent (RP System RP-1AN, manufactured by Mitsubishi Gas Chemical Co., Inc.) was placed on the plunger of the prepared cartridge container, and then a polyethylene sealing film (polyethylene film) was adhered and fixed with an adhesive to the open end of the cartridge main container with the plunger inserted, thereby sealing the opening (injection port) of the cartridge main container in a manner that covers it, thereby preparing a storage container.
  • This fixed polyethylene film is the second sealing structure. Note that this storage container corresponds to the cartridge 20 shown in Figure 2, with the cartridge main container being main container 21a, the plunger being plunger 21b, the polyethylene film being sealing film 22, and the dehydrating and oxygen absorbing agent being member 23.
  • Example 7 A storage container was produced in the same manner as in Example 3, except that no dehydrating or oxygen scavenging agent was added.
  • the storage containers thus prepared were subjected to the following storage stability evaluation.
  • the storage stability evaluation conditions were as follows: the prepared storage container was stored in a thermostatic chamber at a temperature of 40° C. and a humidity of 10 to 50% RH (without humidity control), and the state of the composition in the storage container was observed to evaluate the period during which the composition could maintain a liquid state. That is, the behavior of thickening and gelling of the curable liquid silicone composition was observed by observing the degree to which the composition in the main container followed the tilt of the main container (glass bottle or cartridge container) and flowed (fluidity), and the state in which the fluidity became worse than that immediately after sealing was judged to be thickened or gelled.
  • the storage container in which the curable liquid silicone composition was sealed was stored in a thermostatic chamber, and then observed every 7 days to confirm the time (number of days) until the curable liquid silicone composition thickened or gelled.
  • a second sealing structure polyethylene bag, aluminum-laminated polyethylene bag
  • the main container was made of a metal cartridge main container
  • Table 4 shows the results of evaluating the storage stability (evaluation of storage stability (period during which the liquid state is maintained) at 40° C.) when the compositions (S-1) to (S-4) were enclosed in the storage containers prepared above. It has been confirmed that the storage container of the present invention makes it possible to store an addition-curing liquid silicone composition for long periods of time, such as for example, 42 days or more, and that even after such storage, the platinum catalyst mixture is activated when exposed to air in an unheated, open environment (at room temperature in the atmosphere), causing the addition reaction to proceed and harden into a rubber-like or gel-like form.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Packages (AREA)
  • Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
PCT/JP2023/042752 2022-11-30 2023-11-29 付加硬化型液状シリコーン組成物保存用容器 Ceased WO2024117187A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020257020076A KR20250117391A (ko) 2022-11-30 2023-11-29 부가 경화형 액상 실리콘 조성물 보존용 용기
CN202380082130.1A CN120282917A (zh) 2022-11-30 2023-11-29 加成固化型液体有机硅组合物保存用容器
JP2024561540A JPWO2024117187A1 (https=) 2022-11-30 2023-11-29
EP23897833.2A EP4628423A1 (en) 2022-11-30 2023-11-29 Container for storing addition-curing liquid silicone composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-190866 2022-11-30
JP2022190866 2022-11-30

Publications (1)

Publication Number Publication Date
WO2024117187A1 true WO2024117187A1 (ja) 2024-06-06

Family

ID=91323991

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/042752 Ceased WO2024117187A1 (ja) 2022-11-30 2023-11-29 付加硬化型液状シリコーン組成物保存用容器

Country Status (5)

Country Link
EP (1) EP4628423A1 (https=)
JP (1) JPWO2024117187A1 (https=)
KR (1) KR20250117391A (https=)
CN (1) CN120282917A (https=)
WO (1) WO2024117187A1 (https=)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989667A (en) 1974-12-02 1976-11-02 Dow Corning Corporation Olefinic siloxanes as platinum inhibitors
US3989666A (en) 1974-12-02 1976-11-02 Dow Corning Corporation Crosslinker-platinum catalyst-inhibitor and method of preparation thereof
JPS5987478U (ja) * 1982-11-30 1984-06-13 白井　常雄 容器
US4510094A (en) 1983-12-06 1985-04-09 Minnesota Mining And Manufacturing Company Platinum complex
JPS63218075A (ja) * 1987-03-03 1988-09-12 三菱瓦斯化学株式会社 液状物の保存方法
JPH06192576A (ja) 1992-12-22 1994-07-12 Shin Etsu Chem Co Ltd １液型オルガノポリシロキサン組成物
JPH09143373A (ja) 1995-11-17 1997-06-03 Shin Etsu Chem Co Ltd 付加反応用触媒組成物及び硬化性オルガノポリシロキサン組成物
JPH09141107A (ja) 1995-11-21 1997-06-03 Shin Etsu Chem Co Ltd 白金触媒組成物、その製造方法及び硬化性オルガノポリシロキサン組成物
JP2007217055A (ja) * 2006-02-20 2007-08-30 Dainippon Printing Co Ltd 蓋材およびそれを用いた包装体
JP2009249013A (ja) * 2008-04-09 2009-10-29 Osaka Titanium Technologies Co Ltd シリコン梱包方法
JP2011212366A (ja) * 2010-04-01 2011-10-27 Nippon Soda Co Ltd 二重構造バイアル瓶
WO2022203029A1 (ja) * 2021-03-24 2022-09-29 大日本印刷株式会社 液体入り組合せ容器、容器セットおよび液体入り容器の製造方法
WO2022270366A1 (ja) 2021-06-22 2022-12-29 信越化学工業株式会社 白金触媒混合物、硬化性液状シリコーン組成物及び硬化性液状シリコーン組成物の硬化方法並びに白金触媒混合物の調製方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4811847B2 (ja) 2005-01-11 2011-11-09 三菱鉛筆株式会社 筆記具
JP2009141107A (ja) 2007-12-06 2009-06-25 Seiko Epson Corp レーザ光源装置、プロジェクタおよび光学装置
JP5126666B2 (ja) 2007-12-13 2013-01-23 株式会社デンソー 車両用操作入力装置

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989667A (en) 1974-12-02 1976-11-02 Dow Corning Corporation Olefinic siloxanes as platinum inhibitors
US3989666A (en) 1974-12-02 1976-11-02 Dow Corning Corporation Crosslinker-platinum catalyst-inhibitor and method of preparation thereof
JPS5987478U (ja) * 1982-11-30 1984-06-13 白井　常雄 容器
US4510094A (en) 1983-12-06 1985-04-09 Minnesota Mining And Manufacturing Company Platinum complex
JPS63218075A (ja) * 1987-03-03 1988-09-12 三菱瓦斯化学株式会社 液状物の保存方法
JPH06192576A (ja) 1992-12-22 1994-07-12 Shin Etsu Chem Co Ltd １液型オルガノポリシロキサン組成物
JPH09143373A (ja) 1995-11-17 1997-06-03 Shin Etsu Chem Co Ltd 付加反応用触媒組成物及び硬化性オルガノポリシロキサン組成物
JPH09141107A (ja) 1995-11-21 1997-06-03 Shin Etsu Chem Co Ltd 白金触媒組成物、その製造方法及び硬化性オルガノポリシロキサン組成物
JP2007217055A (ja) * 2006-02-20 2007-08-30 Dainippon Printing Co Ltd 蓋材およびそれを用いた包装体
JP2009249013A (ja) * 2008-04-09 2009-10-29 Osaka Titanium Technologies Co Ltd シリコン梱包方法
JP2011212366A (ja) * 2010-04-01 2011-10-27 Nippon Soda Co Ltd 二重構造バイアル瓶
WO2022203029A1 (ja) * 2021-03-24 2022-09-29 大日本印刷株式会社 液体入り組合せ容器、容器セットおよび液体入り容器の製造方法
WO2022270366A1 (ja) 2021-06-22 2022-12-29 信越化学工業株式会社 白金触媒混合物、硬化性液状シリコーン組成物及び硬化性液状シリコーン組成物の硬化方法並びに白金触媒混合物の調製方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4628423A1

Also Published As

Publication number Publication date
EP4628423A1 (en) 2025-10-08
KR20250117391A (ko) 2025-08-04
CN120282917A (zh) 2025-07-08
JPWO2024117187A1 (https=) 2024-06-06

Similar Documents

Publication Publication Date Title
TWI720245B (zh) 硬化性有機聚矽氧烷組成物及電氣電子零件的保護劑或接著劑組成物
EP2497802B1 (en) Addition curable self-adhesive silicone rubber composition
US8044153B2 (en) Curable silicone composition
EP3431552B1 (en) Addition-curable silicone rubber composition and cured product
JP4430470B2 (ja) 付加反応硬化型シリコーンゴム組成物
KR102313596B1 (ko) 부가 경화성 실리콘 고무 조성물 및 경화물
ES2996689T3 (en) Addition-curable silicone composition and cured silicone rubber
JP7626222B2 (ja) 白金触媒混合物の調製方法
US20090105441A1 (en) Curable Organopolysiloxane Composition
EP1045005A1 (en) Silicone gel composition
TWI853911B (zh) 室溫固化性有機聚矽氧烷組成物及電氣、電子零件之保護劑或黏合劑組成物
WO2022067597A1 (en) Silicone foam elastomers and their uses
JP5482702B2 (ja) ２液混合型オルガノポリシロキサン組成物及び該組成物の硬化方法
WO2024117187A1 (ja) 付加硬化型液状シリコーン組成物保存用容器
EP2851397B1 (en) Curable resin composition and primer composition
WO2022172614A1 (ja) 硬化性シリコーン組成物及び接着剤
KR102780092B1 (ko) 요변성 경화성 실리콘 조성물을 생성하는 방법
JP2007106905A (ja) 加熱硬化型液状シリコーンゴム組成物
CN114630879B (zh) 聚苯硫醚树脂粘接用聚有机硅氧烷组合物
CN118451144A (zh) 固化性液体有机硅组合物和该组合物的固化方法
US20240279468A1 (en) Curable silicone rubber compositions
JP2025120520A (ja) 好気硬化型液状シリコーン組成物の製造方法及び一液保存性の改善方法
KR20250081864A (ko) 액상 부가경화형 플루오로실리콘 조성물, 플루오로실리콘 고무 및 성형품
JPH0578587B2 (https=)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23897833

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024561540

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202380082130.1

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2023897833

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023897833

Country of ref document: EP

Effective date: 20250630

WWP Wipo information: published in national office

Ref document number: 202380082130.1

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020257020076

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2023897833

Country of ref document: EP