Container for storing addition-curable liquid silicone composition

Abstract

The present invention relates to a container for storing an addition-curable liquid silicone composition, and more specifically, to a container for storing an addition-curable liquid silicone composition containing a platinum catalyst which is inactive in an atmosphere having a humidity of 5% RH or less and an oxygen concentration of 0.1 vol% or less and which is activated by contact with the atmosphere, the catalyst is crosslinked and cured by a hydrosilylation addition reaction in the presence of the platinum catalyst activated in the atmosphere. The container comprises: a first sealing structure that serves as a container in which the addition-curable liquid silicone composition is sealed (filled) and that has a sealing part that seals an injection port into which the addition-curable liquid silicone composition has been injected; a second sealing structure which is a film that covers at least the entire sealing part of the first sealing structure or the entire first sealing structure so as to further seal the sealing part; and a member which is provided between the first sealing structure and the second sealing structure and has a function of consuming and removing oxygen and moisture. The present invention makes it possible to improve the storability of an addition-curable liquid silicone composition having gas-requiring curability.

Description

Technical Field

[0001] 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), which contains an aerobic platinum catalyst mixture that is activated by contact with moisture (humidity) and / or oxygen in the atmosphere to catalyze a hydrosilylation addition reaction, and can be cured to form a silicone rubber cured product (organosilicon elastomer) or a silicone gel cured product. Background Art

[0002] In view of energy conservation and requirements for SDGs (Sustainable Development Goals), the requirement to cure a liquid silicone composition without heating has been further strengthened in recent years. In addition, for easy use of materials and further for the purpose of preventing mistakes during use, a one-component type of material is preferred.

[0003] Among liquid-curing silicone compositions, as one-component type and crosslinking reaction type silicone compositions that can be cured without heating, there are condensation reaction type, ultraviolet radical reaction type, or addition reaction type silicone compositions. Among these, there are silicone compositions that significantly shorten the shelf life, and silicone compositions that can activate the catalyst with ultraviolet light to cure it. However, they are all insufficient in deep curability during curing or curability in the ultraviolet shadow (area not reached by ultraviolet light), and there are limitations in the applications where they can be used. In addition, when ultraviolet irradiation is required, a large amount of electric energy is required for it.

[0004] In the technology of curing a silicone composition into a rubber or gel state by using a crosslinking reaction applying an addition reaction based on a platinum catalyst, in technologies aiming at one-component storage stability of the unreacted composition or ensuring the pot life and curing at a lower temperature, there are the following prior arts (U.S. Patent No. 3,989,666, U.S. Patent No. 3,989,667, U.S. Patent No. 4,510,094, Japanese Patent Laid-Open No. 9-143373, Japanese Patent Laid-Open No. 6-192576, Japanese Patent Laid-Open No. 9-141107 (Patent Documents 1 to 6)), but none of them can achieve both airtight one-component storage stability at the marketable circulation level and room temperature curing after opening.

[0005] In contrast, in International Publication No. 2022 / 270366 (Patent Document 7), a one-component type, aerobic curable addition-curing type liquid silicone composition is proposed, which remains in a liquid state in a substantially deoxygenated and dehydrated sealed container and can react and cure by opening the container to contact with the atmosphere.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Specification of U.S. Patent No. 3,989,666

[0009] Patent Document 2: Specification of U.S. Patent No. 3,989,667

[0010] Patent Document 3: Specification of U.S. Patent No. 4,510,094

[0011] Patent Document 4: Japanese Patent Laid-Open No. 9-143373

[0012] Patent Document 5: Japanese Patent Laid-Open No. 6-192576

[0013] Patent Document 6: Japanese Patent Laid-Open No. 9-141107

[0014] Patent Document 7: International Publication No. 2022 / 270366 Summary of the Invention

[0015] Problems to be Solved by the Invention

[0016] However, when such a one-component and air-curing addition-curing type liquid silicone composition is stably circulated in the market, it is necessary to store and transport the composition in a state where oxygen and moisture are completely blocked. As a result, for existing containers, oxygen and moisture invading from the container raw material itself or the container lid part cannot be completely blocked, and sometimes the storage stability of the content (air-curing addition-curing type liquid silicone composition) becomes insufficient.

[0017] The present invention has been completed in view of the above actual situation, and an object thereof is to provide a container for storing an addition-curing type liquid silicone composition that improves the storage stability of a one-component and air-curing addition-curing type liquid silicone composition.

[0018] Means for Solving the Problems

[0019] The inventors of the present invention conducted in-depth research to solve the above problems and found that: as a container for storing an air-curing addition-curing type liquid silicone composition, by including a first sealing structure that fills the addition-curing type liquid silicone composition and has a sealing part that seals the injection port of the composition, and a second sealing structure that further seals the sealing part, and forming a structure in which a function of deoxidizing and dehydrating is imparted to the space (void) between the first sealing structure and the second sealing structure, the storage stability of the air-curing liquid silicone composition in the first sealing structure, particularly an addition-curing type liquid silicone composition containing an aerobic platinum catalyst, can be significantly improved.

[0020] Therefore, the present invention provides a container (packaging form) for storing an addition-curable liquid silicone composition as described below.

[0021] [1] The container for storing an addition-curable liquid silicone composition is a container for storing an addition-curable liquid silicone composition, wherein the addition-curable liquid silicone composition contains a platinum catalyst 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 and is activated by contact with the atmosphere, and is crosslinked and cured by a hydrosilylation addition reaction in the presence of the platinum catalyst activated in the atmosphere.

[0022] It includes: a first sealing structure that is a container for enclosing the addition-curable liquid silicone composition and has a sealing portion formed by sealing an injection port for injecting the addition-curable liquid silicone composition, 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, and a member provided between the first sealing structure and the second sealing structure and having a function of consuming and removing oxygen and moisture.

[0023] [2] The container for storing an addition-curable liquid silicone composition according to [1], wherein the addition-curable liquid silicone composition contains the following components (A) to (C).

[0024] (A) A diorganopolysiloxane having at least one alkenyl group in one molecule.

[0025] (B) An organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: the amount is such that, relative to each 1 mole of the alkenyl group in component (A), the hydrogen atoms bonded to silicon atoms (SiH groups) in component (B) are 0.5 to 4 moles.

[0026] (C) A platinum catalyst mixture that becomes active by oxygen and / or moisture: the amount is such that, in terms of the mass of platinum atoms in component (C) relative to the total mass of components (A) and (B), it is 0.1 to 1000 ppm.

[0027] [3] The container for storing an addition-curable liquid silicone composition according to [2], wherein the platinum catalyst mixture is an aerobic platinum catalyst mixture composed of a reaction mixture of a platinum-containing alkenyl group-containing organosiloxane complex and an organosilicon compound having at least one SiH group in the molecule, and the amount of the organosilicon compound is such that the hydrogen atoms bonded to silicon atoms (SiH groups) are in an excess molar amount relative to the alkenyl group in the platinum-containing alkenyl group-containing organosiloxane complex.

[0028] [4]The container for storing the addition-curable liquid silicone composition according to [3], wherein the platinum-vinyl group-containing organosiloxane complex is a complex of platinum, platinum chloride, chloroplatinic acid or chloroplatinate and a vinyl group-containing siloxane.

[0029] [5]The container for storing the addition-curable liquid silicone composition according to [4], wherein the vinyl group-containing siloxane is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0030] [6]The container for storing the addition-curable liquid silicone composition according to any one of [3] to [5], wherein the organosilicon compound having at least one hydrogen atom bonded to a silicon atom is an organohydrogensilane or an organohydrogensiloxane oligomer.

[0031] [7]The container for storing the 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 selected from 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.

[0032] [8]The container for storing the 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 at least two hydrogen atoms (SiH groups) each bonded to a silicon atom in the molecule, and the silicon atoms are adjacent to each other through an oxygen atom forming a siloxane bond (Si-O-Si).

[0033] [9]The container for storing the addition-curable liquid silicone composition according to any one of [1] to [8], wherein the first sealing structure is composed of a container of metal, glass, ceramic or resin, and the sealing part is a sealing part formed by inserting, fitting or screwing a lid part composed of metal, glass, ceramic or resin into the injection port into which the addition-curable liquid silicone composition is injected or bonding or welding the injection port itself to seal the injection port.

[0034]

[10] The container for storing the addition-curable liquid silicone composition according to any one of [1] to [9], wherein the second sealing structure includes a resin film.

[0035]

[11] The container for storing an addition-curable liquid silicone composition according to any one of [1] to [9], wherein the second sealing structure includes a laminated structure film of a resin layer and a metal layer or a laminated structure film of a metal foil and a metal layer.

[0036]

[12] The container for storing an addition-curable liquid silicone composition according to any one of [1] to

[11] , wherein the second sealing structure is heat-fused or adhered to the outer peripheral portion of the first sealing structure of the at least entire sealing portion of the first sealing structure in a state of covering the same, so as to further seal the sealing portion.

[0037]

[13] The container for storing an addition-curable liquid silicone composition according to any one of [1] to

[11] , wherein the second sealing structure is hermetically sealed by heat fusion or adhesion in a state of covering all of the first sealing structure, so as to further seal the sealing portion.

[0038]

[14] The container for storing an addition-curable liquid silicone composition according to any one of [1] to

[13] , wherein the member having a function of consuming and removing oxygen and moisture is composed of a dehydration and deoxidizer, or a combination of a dehydrating agent and a deoxidizer.

[0039]

[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 gap between the first sealing structure and the second sealing structure.

[0040]

[16] The container for storing an addition-curable liquid silicone composition according to any one of [1] to

[15] , wherein the member having a function of consuming and removing oxygen and moisture is disposed on the sealing portion of the first sealing structure.

[0041]

[17] The container for storing an addition-curable liquid silicone composition according to any one of [1] to

[16] , wherein the function of consuming and removing oxygen and moisture of the member having a function of consuming and removing oxygen and moisture is a function of chemically reacting with oxygen and moisture in the space where the member is present to absorb them.

[0042] Effects of the Invention

[0043] The storage container according to the present invention is for a gas-curable liquid silicone composition, particularly a one-component addition-curing liquid silicone composition containing a platinum catalyst mixture that is activated by contact with moisture and / or oxygen in the atmosphere to catalyze a hydrosilylation addition reaction (i.e., having sufficient "long-term one-component storage property in a closed container for storing and transporting materials" at refrigerated to room temperature, and when the material is used, without heating and in an open state (i.e., by contacting moisture and / or oxygen in the atmosphere at room temperature), "activating the gas-required platinum catalyst mixture contained in the composition, allowing the hydrosilylation addition reaction to proceed, and rapidly curing not only the air-contact surface but also the deep part" of the material). Its storage and storage properties are further improved, the flexibility of transportation can be enhanced, and it can contribute to the supply of various components and products that save energy and are in line with the SDGs. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 FIG. (a) is a schematic diagram showing the structure of a can as a first embodiment of the storage container for the addition-curing liquid silicone composition according to the present invention, and FIG. (b) is a cross-sectional view of the main part of this embodiment.

[0045] Figure 2 FIG. is a schematic cross-sectional view showing the structure of a box as a second embodiment of the storage container for the addition-curing liquid silicone composition according to the present invention.

[0046] Figure 3 FIG. (a) is a schematic diagram showing the structure of a package (1) as a third embodiment of the storage container for the addition-curing liquid silicone composition according to the present invention before being hermetically sealed with a second sealing structure, and FIG. (b) is a schematic diagram showing the structure after being hermetically sealed with a second sealing structure.

[0047] Figure 4 FIG. is a schematic diagram showing the structure of a package (2) as a fourth embodiment of the storage container for the addition-curing liquid silicone composition according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0048] In the present invention, the so-called "aerophilic property" refers to the property (aerophilic reaction type) of a catalyst (especially a platinum catalyst) that is a catalyst for hydrosilylation addition reaction and is in a state of low catalytic activity in a closed state with a low oxygen concentration (substantially anaerobic) and a low moisture content where contact with moisture (humidity) and oxygen is blocked, and is activated by contact with moisture (humidity) and / or oxygen in the atmosphere. The so-called "aerophilic curability" refers to the property of an addition-curable liquid silicone composition of the addition-curing type that does not undergo a hydrosilylation addition reaction (does not cure) in a closed state with a low oxygen concentration and a low moisture content where contact with moisture (humidity) and oxygen is blocked, and promotes the hydrosilylation addition reaction and cures when in contact with the atmosphere. In addition, the so-called closed state (or under closed conditions) refers to a state where contact with the atmosphere is blocked (i.e., contact with moisture (humidity) and oxygen is blocked), and a closed container refers to a container that achieves this closed state. In addition, the "atmosphere" mentioned here is premised on an oxygen concentration of 21% by volume, a humidity greater than 5% RH and 100% RH or less. The low oxygen concentration in the closed state means an oxygen concentration of 0.1% by volume or less, and the low moisture content means a humidity of 5% RH or less.

[0049] Among them, the addition-curable liquid silicone composition to be preserved in the present invention is an addition-curable liquid silicone composition that contains a platinum catalyst 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 and is activated by contact with the atmosphere, and undergoes crosslinking and curing by the hydrosilylation addition reaction in the presence of this platinum catalyst activated in the atmosphere. The so-called addition-curable liquid silicone composition with aerophilic curability is preferably, for example, the composition shown in Patent Document 7. In a closed state with a low oxygen concentration and a low moisture content where contact with the atmosphere is blocked, the activity of the platinum catalyst, which is a curing reaction catalyst, is low, and the composition remains liquid without curing. On the other hand, when opened to the atmosphere, the platinum catalyst is activated by oxygen and / or moisture in the atmosphere, and crosslinking and curing are rapidly carried out through the hydrosilylation addition reaction, and a desired cured product (such as a silicone rubber cured product, a silicone gel cured product, etc.) can be obtained.

[0050] When such an addition-curable liquid silicone composition curable with air is distributed and sold, in the case of existing packaging forms (storage containers), it is impossible to prevent the intrusion of oxygen and moisture from the external atmosphere, and sometimes the storage stability of the product becomes insufficient. Further, as a similar curable silicone composition, there is a condensation-curable silicone composition that reacts and cures by utilizing moisture from the atmosphere. In this case, there are various methods for improving the storage stability of the condensation-curable silicone composition by preventing the intrusion of moisture from the external atmosphere. Since the curability of such a condensation-curable silicone composition is not affected by oxygen, as a method for improving the storage stability, preventing the intrusion of oxygen is not considered, and as a means for packaging the addition-curable liquid silicone composition curable with air, which is the object of the present invention, it is not sufficient.

[0051] The present inventors conducted in-depth research to solve this problem.

[0052] First, for the rational production of an addition-curable liquid silicone composition curable with air, it is necessary to quickly fill the prepared composition into a filling container and then seal it inside the filling container. At this time, in order to quickly seal the filling container, the structure of inserting, fitting, or screwing a lid portion into the injection port into which the addition-curable liquid silicone composition has been injected or bonding or heat-sealing the injection port itself is used to seal the injection port. However, for the raw materials and structure of this sealed portion (sealing portion), especially the structure of inserting, fitting, or screwing a lid portion, the intrusion of oxygen and moisture from the external atmosphere cannot be completely prevented at the sealing portion.

[0053] Therefore, it was found that by using the above-mentioned filling container as a first sealing structure body and covering at least the entire sealing portion of the first sealing structure body or the entire first sealing structure body with a second sealing structure body (film) for further sealing, and further providing a member (an oxygen and moisture removing mechanism) having a function of consuming and removing oxygen and moisture in the space between the first sealing structure body and the second sealing structure body, it is possible to substantially eliminate the intrusion of oxygen and moisture from the external atmosphere into the addition-curable liquid silicone composition in the container, and the container for storing the addition-curable liquid silicone composition of the present invention was completed.

[0054] <Container for storing addition-curable liquid silicone composition>

[0055] That is, the container for storing an addition-curing type liquid silicone composition of the present invention is a container for storing an addition-curing type liquid silicone composition, the addition-curing type liquid silicone composition contains a platinum catalyst 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 and is activated by contact with the atmosphere, and is crosslinked and cured by a hydrosilylation addition reaction in the presence of the platinum catalyst activated in the atmosphere. The container includes: (1) a first sealing structure that is a container for enclosing (filling) the addition-curing type liquid silicone composition and has a sealing portion formed by sealing an injection port for injecting the addition-curing type liquid silicone composition; (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; and (3) a member having a function of consuming and removing oxygen and moisture provided between the first sealing structure and the second sealing structure.

[0056] Among them, the first sealing structure is a container for enclosing the above-mentioned addition-curing type liquid silicone composition, and is preferably composed of a container made of metal, glass, ceramic or resin. Further, as the metal that is the raw material for forming the first sealing structure, aluminum, iron, stainless steel, etc. can be cited, as the ceramic, alumina, etc. can be cited, and as the resin, synthetic resins such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride can be cited. In addition, the first sealing structure only needs to ensure the strength as the first sealing structure and have a thickness to the extent that the atmosphere (i.e., oxygen and moisture) does not permeate.

[0057] In addition, as the form of the container of the first sealing structure, it can be selected from cans, bottles, tubes, boxes, etc. according to the physical properties (viscosity, etc.) and uses (usage methods) of the filled addition-curing type liquid silicone composition.

[0058] The first sealing structure has a sealing portion formed by sealing an injection port into which the above-mentioned addition-curing type liquid silicone composition is injected. That is, in the container of the first sealing structure, an injection port for initially injecting the above-mentioned addition-curing type liquid silicone composition is provided. The addition-curing type liquid silicone composition is injected from this injection port, and after filling in the container of the first sealing structure, the injection port is sealed, and it becomes a sealing portion.

[0059] The sealing part is preferably a sealing part formed by inserting, fitting or screwing a cover part made of metal, glass, ceramic or resin into the injection port into which the addition curing liquid silicone composition is injected, or by bonding or welding (thermal welding) the injection port itself to seal the injection port. The material of the cover part can be the same as the raw material constituting the above-mentioned first sealing structure. As metals, aluminum, iron, stainless steel, etc. can be listed, as ceramics, aluminum oxide, etc. can be listed, and as resins, synthetic resins such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride can be listed.

[0060] The first sealing structure may be a container for storing a conventional addition-curable liquid silicone composition.

[0061] 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. Furthermore, the so-called covering at least the entire sealing portion of the first sealing structure means that the second sealing structure covers the entire sealing portion of the first sealing structure to further seal it and can also cover its peripheral portion.

[0062] The second sealing structure is preferably composed of a resin film, preferably a laminated structure film of a resin layer and a metal layer, or a laminated structure film of a metal foil and a metal layer. Among them, in terms of the strength, flexibility and low permeability of the film, a laminated structure film of a resin layer (film) and a metal layer (foil) is preferred, and in particular, in the second sealing structure, it is more preferred that the metal layer (foil) of the laminated structure film is the outer surface.

[0063] The resin constituting the film serving as the second sealing structure is preferably a synthetic resin such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, etc. The metal constituting the metal layer or the metal foil is preferably aluminum.

[0064] In addition, the second sealing structure can ensure the strength of the second sealing structure and have a thickness that can suppress the penetration of the atmosphere (i.e., oxygen and moisture) as much as possible. In the case of a resin film, the thickness is preferably 10 to 1000 μm. In the case of a laminated structure film, the thickness of the resin layer or metal foil that becomes the substrate is preferably 10 to 1000 μm, and the thickness of the laminated metal layer is preferably 5 to 50 μm.

[0065] As a method of further sealing with the second sealing structure, examples include fixing a film-shaped second sealing structure to the outer peripheral portion of the sealing portion of the first sealing structure using an adhesive or heat welding, or after housing the entire first sealing structure inside a bag-shaped second sealing structure, sealing the opening portion of the second sealing structure using heat welding or the like. That is, it is preferable that the second sealing structure is heat welded or adhered to the first sealing structure on the outer peripheral portion of the sealing portion in a state where at least the entire sealing portion of the first sealing structure is covered, so as to further seal the sealing portion. Alternatively, it is preferable that the second sealing structure is hermetically sealed by heat welding or adhesion in a state where the second sealing structure covers the entire first sealing structure, so as to further seal the sealing portion.

[0066] In the container for storing the addition-curable liquid silicone composition of the present invention, in a state where the addition-curable liquid silicone composition is doubly sealed inside the first sealing structure, 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 member having a function of consuming and removing oxygen and moisture preferably chemically reacts with the oxygen and moisture in the space where the member exists, thereby absorbing them. Thus, by reducing the oxygen and moisture in the space (void) between the first sealing structure and the second sealing structure, it is possible to prevent oxygen and moisture from invading the first sealing structure.

[0067] Among them, it is preferable to provide a void between the first sealing structure and the second sealing structure, and a member having a function of consuming and removing oxygen and moisture is provided in this void. At this time, it is more preferable to dispose the member having a function of consuming and removing oxygen and moisture on the sealing portion of the first sealing structure. In addition, the member having a function of consuming and removing oxygen and moisture can be fixed to the sealing portion of the first sealing structure.

[0068] In addition, it is preferable that the function of consuming and removing oxygen and moisture of the member having a function of consuming and removing oxygen and moisture is to chemically react with the oxygen and moisture in the space where the member exists to absorb them. That is, in order to efficiently absorb the oxygen and moisture in the space (void) between the first sealing structure and the second sealing structure, from the aspects of cost and performance, it is preferable that the member having a function of consuming and removing oxygen and moisture is, for example, a member composed of a so-called irreversible dehydrating and deoxidizing agent such as a member using a reaction in which metal iron powder or the like is oxidized by oxygen and moisture to become ferrous oxide or iron oxide, a member using an exothermic reaction of calcium oxide with oxygen and a reaction of forming calcium hydroxide with water. In addition, as a member composed of a combination of a dehydrating agent and a deoxidizing agent, it is also possible to absorb oxygen and moisture with different members respectively.

[0069] Components with the function of consuming and removing oxygen and moisture can use commercially available products. For example, as dehydration and deoxidation agents, RP series products such as RP-1AN, RP-3AN, RP-5AN, RP-10AN, etc. (manufactured by Mitsubishi Gas Chemical Company, Inc.) can be cited. As a combination of a dehydration agent and a deoxidation agent, a combination of Ageless Dry ADN series (such as ADN-5, etc.) (manufactured by Mitsubishi Gas Chemical Company, Inc.) as a dehydration agent (desiccant) and Ageless (type S, etc.) (manufactured by Mitsubishi Gas Chemical Company, Inc.) as a self-reacting iron-based deoxidation agent can be cited. The components with the function of consuming and removing oxygen and moisture can be packaged in a manner that does not hinder the respective functions of these dehydration and deoxidation agents, or the dehydration agent and the deoxidation agent.

[0070] The amount of the component with the function of consuming and removing oxygen and moisture, that is, the amount of the dehydration and deoxidation agents, and the amounts of the dehydration agent and the deoxidation agent in the component composed of the combination of the dehydration agent and the deoxidation agent only need to be the amounts required for effectively absorbing the oxygen and moisture between the first sealing structure and the second sealing structure (void), and can be appropriately set.

[0071] For the container for storing the addition-curable liquid silicone composition according to the present invention, a sealing portion that seals the opening of the first sealing structure during storage is formed, and the second sealing structure is further used for sealing, suppressing the inflow of the atmosphere (that is, oxygen and moisture) into this sealing portion. In addition, a component with the function of consuming and removing oxygen and moisture provided between the first sealing structure and the second sealing structure is further used to remove the oxygen and moisture in the narrow space (void) between the sealing portion and the second sealing structure. Therefore, the inflow of oxygen and moisture into the sealing portion is further suppressed. Thus, the storage stability and storage property of the addition-curable liquid silicone composition that requires air curing are further improved, and the flexibility of transportation can be improved.

[0072] The present invention will be described in more detail based on the accompanying drawings below.

[0073] (Tank (tank: tank))

[0074] The tank in the present invention is a metal sealed container (tank: tank) for storing and transporting the addition-curable liquid silicone composition.

[0075] In Figure 1 shows the structure of the tank as the first embodiment of the container for storing the addition-curable liquid silicone composition according to the present invention. Figure 1 (a) is a structural diagram of the whole container, Figure 1 (b) is a cross-sectional view of the main part of this embodiment.

[0076] The tank 10 as the container for storing the addition-curable liquid silicone composition according to the present invention is asFigure 1 As shown in Fig. (a), it mainly consists of a main container 11a in the shape of a box.

[0077] In Figure 1 Fig. (b) shows Figure 1 the cross-section of the part surrounded by a dashed line in Fig. (a).

[0078] On the upper surface of the main container 11a, at the place surrounded by a dashed line, an opening 11h is provided as an injection port for injecting an addition-curing type liquid silicone composition. After the addition-curing type liquid silicone composition is injected, the opening 11h is sealed (sealing part) by inserting, fitting or screwing a lid part 11b. The main container 11a and the lid part 11b constitute the above-mentioned first sealing structure.

[0079] The main container 11a and the lid part 11b are preferably made of metals such as aluminum, iron, and stainless steel.

[0080] The sealing film 12, as the above-mentioned second sealing structure, is a sheet that covers the whole part (the sealing part of the first sealing structure) where the opening 11h of the main container 11a (that is, the injection port for injecting the addition-curing type liquid silicone composition) is sealed by the lid part 11b and further seals the sealing part. In particular, in the can 10, it is preferably fixed by heat-sealing or bonding the sealing film 12 at the opening end of the main container 11a so as to further seal the sealing part in a manner of covering the opening (injection port) of the main container 11a. At this time, it is more preferable to degas the space between the part (the sealing part of the first sealing structure) where the opening 11h of the main container 11a is sealed by the lid part 11b and the sealing film 12 and then fix the sealing film 12. The sealing film 12 is preferably a film made of a synthetic resin such as polyethylene, or a laminated film in which a film of a synthetic resin such as polyethylene is laminated with a metal film or a metal thin film such as aluminum.

[0081] The member 13 is a member having the function of consuming and removing oxygen and moisture as described above, and is preferably provided in the gap between the part (the sealing part of the first sealing structure) where the opening 11h of the main container 11a is sealed by the lid part 11b and the sealing film 12, and more preferably fixed on the upper surface of the lid part 11b.

[0082] The can 10 according to the present invention forms a sealing portion where the opening 11h of the main container 11a is sealed by the lid portion 11b during storage, and then is further sealed with the sealing film 12, suppressing the inflow of the atmosphere (i.e., oxygen and moisture) into this sealing portion. In addition, the oxygen and moisture in the narrow space (void) between the sealing portion and the sealing film 12 are removed by the member 13 provided between the lid portion 11b and the sealing film 12, so the inflow of oxygen and moisture into the sealing portion is further suppressed. Therefore, the storage property and storage stability of the air-curable addition-curable liquid silicone composition are further improved, and the flexibility of transportation can be improved. In addition, when using the addition-curable liquid silicone composition, after removing the sealing film 12 and the member 13 from the can 10, by opening the lid portion 11b, the addition-curable liquid silicone composition can be easily taken out, and by closing the lid portion 11b, it can also be temporarily sealed.

[0083] (Cartridge)

[0084] The cartridge in the present invention is also called a cartridge for sealant. It stores the addition-curable liquid silicone composition enclosed inside, and at the same time installs a cartridge gun (caulking gun), and discharges the addition-curable liquid silicone composition from the nozzle portion provided at the top end of the cartridge main container, and is used in construction operations such as sealing.

[0085] In Figure 2 FIG. shows a cross-sectional schematic view of a cartridge as a second embodiment of the container for storing the addition-curable liquid silicone composition according to the present invention.

[0086] The cartridge 20 as the container for storing the addition-curable liquid silicone composition according to 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 as the above-mentioned second sealing structure, and a member 23 as the above-mentioned member having the function of consuming and removing oxygen and moisture. The main container 21a, the nozzle portion 21n, and the plunger 21b constitute the above-mentioned first sealing structure.

[0087] The main container 21a is a cylindrical container. A nozzle portion 21n for discharging the addition-curable liquid silicone composition 1 is provided at one end thereof, and the other end is an opening open to the outside, serving as an injection port for injecting the addition-curable liquid silicone composition 1. After the addition-curable liquid silicone composition 1 is injected, the injection port (sealing portion) is sealed by the plunger 21b provided inside thereof.

[0088] The nozzle part 21n provided at the top end of the main body container 21a is a container integrated with the main body container 21a during the storage of the cartridge 20. When in use of the cartridge 20, if a part of it is cut with a cutter or the like, a discharge hole is formed, and the addition-curing type liquid silicone composition 1 filled in the main body container 21a can be discharged to the outside from the discharge hole formed in the nozzle part.

[0089] The plunger 21b inserted into the end of the main body container 21a is arranged to slide freely along the inner surface of the main body container 21a. In a state where at least a part of the outer peripheral surface of the plunger 21b abuts against the inner peripheral surface of the main body container 21a, by using the extrusion pressure from a cartridge gun (caulking gun), it moves along the inner surface of the main body container 21a in the direction of the nozzle part 21n at the top end. As a result, the addition-curing type liquid silicone composition 1 in the main body container 21a is extruded by the plunger 21b and discharged to the outside through the discharge port of the nozzle part 21n. On the cylindrical inner peripheral surface of the main body container 21a, it is preferable to provide a coating film that enables the plunger 21b to move easily while sliding with the inner peripheral surface, and at the same time inhibits the inflow of air from the outside between the cylindrical inner peripheral surface of the main body container 21a and the outer peripheral surface of the plunger 21b.

[0090] The main body container 21a, the nozzle part 21n, and the plunger 21b are preferably made of synthetic resin such as polyethylene. The main body container 21a can be made of metal such as aluminum.

[0091] The sealing film 22, as the above-mentioned second sealing structure, is a sheet-like member that covers the entire part (the sealing part of the first sealing structure) that seals the opening of the main body container 21a (that is, the injection port into which the addition-curing type liquid silicone composition 1 is injected) with the plunger 21b and further seals this sealing part. In particular, in the cartridge 20, it is preferable to fix the sealing film 22 by heat welding or bonding at the opening end of the main body container 21a to further seal the opening (injection port) of the main body container 21a in a manner of covering the lid. At this time, it is more preferable to degas the space between the part (the sealing part of the first sealing structure) that seals the opening of the main body container 21a with the plunger 21b and the sealing film 22 and then fix the sealing film 22. The sealing film 22 is preferably a film made of synthetic resin such as polyethylene, or a laminated film in which a film of synthetic resin such as polyethylene is laminated with a metal film or a metal thin film such as aluminum.

[0092] The member 23 is a member having the function of consuming and removing oxygen and moisture, and is preferably arranged in the gap between the part (the sealing part of the first sealing structure) that seals the opening of the main body container 21a with the plunger 21b and the sealing film 22, and more preferably fixed on the upper surface of the plunger 21b.

[0093] According to the cartridge 20 of the present invention, after forming a sealing portion that seals the opening of the main container 21a with the plunger 21b during storage, further sealing is performed with the sealing film 22, which suppresses the inflow of air (i.e., oxygen and moisture) into the sealing portion. In addition, by using the member 23 having a function of consuming and removing oxygen and moisture provided between the plunger 21b and the sealing film 22, oxygen and moisture in the narrow space (void) between the sealing portion and the sealing film 22 are further removed. Therefore, the inflow of oxygen and moisture into the sealing portion is further suppressed. Thus, the storage stability and storage property of the addition-curable liquid silicone composition that requires air curing are further improved, and the flexibility of transportation can be enhanced. In addition, when using the addition-curable liquid silicone composition, after removing the sealing film 22 and the member 23 from the cartridge 20, by installing a cartridge gun, the addition-curable liquid silicone composition can be easily applied.

[0094] (Packaging (packaging container))

[0095] The packaging in the present invention is a method of covering and sealing the entire first sealing structure, which is a container such as a can, a cartridge, or a bag, with a film-like second sealing structure (packaging container).

[0096] In Figure 3 shows the structure of the packaging (1) as the third embodiment of the container for storing the addition-curable liquid silicone composition according to the present invention. Figure 3 (a) is a configuration diagram before being hermetically sealed with the second sealing structure, Figure 3 (b) is a configuration diagram after being hermetically sealed with the second sealing structure.

[0097] The packaging 30 for storing the addition-curable liquid silicone composition according to the present invention includes: a main container 31 filled with the addition-curable liquid silicone composition 1 as the above-mentioned first sealing structure, a sealing film 32 as the above-mentioned second sealing structure that covers the entire main container 31 and the member 33, and the above-mentioned member 33 having a function of consuming and removing oxygen and moisture.

[0098] The main container 31 is a cylindrical container filled with the addition-curable liquid silicone composition 1 and has a sealing portion (not shown) that seals the injection port into which the addition-curable liquid silicone composition 1 is injected. The main container 31 is composed of, for example, the main container 21a, the nozzle portion 21n, and the plunger 21b in the above-mentioned cartridge 20.

[0099] The sealing film 32 covers and seals the entire main container 31 and the member 33 and is preferably composed of a film made of a synthetic resin such as polyethylene, or a laminated film in which a film made of a synthetic resin such as polyethylene is laminated with a metal film or a metal thin film such as aluminum.

[0100] The component 33 is the above-described component having the function of consuming and removing oxygen and moisture, and is preferably fixed to the upper surface of the main container 31 having a sealing portion.

[0101] By first accommodating the main container 31 filled with the addition-curable liquid silicone composition 1 and the component 33 disposed on the upper surface of the main container 31 in a bag-shaped sealing film 32a having an opening portion ( Figure 3 (a)), the entire circumference near the bag opening portion of the sealing film 32a is bonded or heat-sealed so that the bag opening portion becomes the sealing portion 32s, whereby the package 30 can be manufactured ( Figure 3 (b)). At this time, it is preferable to perform degassing in the sealing film 32a and then perform bonding or heat-sealing. The sealing film 32 hermetically seals the main container 31 and the component 33. Further, the sealing film 32a may be a so-called bag container formed by laminating two sheet-like films and bonding or heat-sealing three sides thereof.

[0102] In the package 30 according to the present invention, after forming a sealing portion that seals the opening portion of the main container 31 during storage, the sealing film 32 is further used for sealing, thereby suppressing the inflow of the atmosphere (i.e., oxygen and moisture) into the sealing portion. In addition, further using the component 33 having the function of consuming and removing oxygen and moisture provided between the main container 31 and the sealing film 32, the oxygen and moisture in the space (void) between the sealing portion and the sealing film 32 are removed, so that the inflow of oxygen and moisture into the sealing portion is further suppressed. Therefore, the storage stability and storage property of the air-curable addition-curable liquid silicone composition 1 are further improved, and the flexibility of transportation can be improved. Further, when using the addition-curable liquid silicone composition, the sealing film 32 is torn and opened, and after removing the sealing film 32 and the component 33, the main container 31 can be used for a specified purpose.

[0103] In Figure 4 shows the configuration of the package (2) as the fourth embodiment of the container for storing the addition-curable liquid silicone composition according to the present invention.

[0104] The package 40 for storing the addition-curable liquid silicone composition according to the present invention includes: a main container 41 made of a film as the above-described first sealing structure filled with the addition-curable liquid silicone composition 1, a sealing film 42 covering the entire main container 41 and the component 43 as the above-described second sealing structure, and the above-described component 43 having the function of consuming and removing oxygen and moisture.

[0105] The main body container 41 is a packaging container filled with the film raw material of the addition-curable liquid silicone composition 1, and is preferably composed of a film made of a synthetic resin such as polyethylene, or a laminated film formed by laminating a film of a synthetic resin such as polyethylene and a metal film or a metal thin film such as aluminum. In addition, the main body container 41 is initially a bag-shaped container, and has a sealing portion 41s formed by bonding or heat-sealing an injection port (the entire circumference of the bag opening portion) into which the addition-curable liquid silicone composition 1 is injected. Further, the main body container 41 can be a so-called bag container formed by joining two sheet-like films and bonding or heat-sealing their four sides.

[0106] The sealing film 42 covers and seals the entire main body container 41 and the member 43, and is preferably composed of a film made of a synthetic resin such as polyethylene, or a laminated film formed by laminating a film of a synthetic resin such as polyethylene and a metal film or a metal thin film such as aluminum.

[0107] The member 43 is a member having the function of consuming and removing oxygen and moisture as described above, and is preferably fixed near the sealing portion 41s of the main body container 41.

[0108] By first accommodating the main body container 41 filled with the addition-curable liquid silicone composition 1 and the member 43 disposed near the sealing portion 41s of the main body container 41 in a bag-shaped sealing film having an opening portion, and bonding or heat-sealing all the peripheries near the bag opening portion of the bag-shaped sealing film so that the bag opening portion becomes a sealing portion 42s, the package 40 can be manufactured. At this time, it is preferable to degas the inside of the bag-shaped sealing film and then bond or heat-seal it, and the sealing film 42 hermetically seals the main body container 41 and the member 43. Further, the bag-shaped sealing film can be a so-called bag container formed by joining two sheet-like films and bonding or heat-sealing their three sides.

[0109] In the package 40 according to the present invention, after forming the sealing portion 41s that seals the opening portion of the main body container 41 during storage, it is further sealed with the sealing film 42, suppressing the inflow of air (i.e., oxygen and moisture) into the sealing portion. In addition to this, by further using the member 43 having the function of consuming and removing oxygen and moisture provided between the main body container 41 and the sealing film 42 to remove oxygen and moisture in the space (gap) between the sealing portion 41s and the sealing film 42, the inflow of oxygen and moisture into the sealing portion 41s is further suppressed. Therefore, the storage stability and storage property of the air-curable addition-curable liquid silicone composition 1 are further improved, and the flexibility of transportation can be improved. In addition, when using the addition-curable liquid silicone composition, the sealing film 42 is torn and opened, and after removing the sealing film 42 and the member 43, the main body container 41 can be used for a specified purpose.

[0110] [Addition-curable liquid silicone composition]

[0111] Preferred examples of the addition-curable liquid silicone composition (addition-curable liquid silicone rubber composition or addition-curable liquid silicone gel composition) to be stored in the present invention include compositions obtained by mixing components (A) to (C) described below and other components as required.

[0112] [(A) Alkenyl-containing diorganopolysiloxane]

[0113] The alkenyl-containing diorganopolysiloxane of the component (A) is a linear or branched diorganopolysiloxane having at least one, preferably two or more alkenyl groups in one molecule, and functions as a main agent (base polymer) of the addition-curable liquid silicone composition (hereinafter also referred to as the composition of the present invention) to be stored in the present invention. Generally, it is a linear diorganopolysiloxane in which the main chain portion is basically composed of repeating diorganosiloxane units and both ends of the molecular chain are blocked with triorganosiloxy groups. It may be a branched diorganopolysiloxane having a branched structure in a part of the siloxane structure constituting the molecular chain.

[0114] The alkenyl-containing diorganopolysiloxane of the component (A) has at least one (usually 1 to 50), preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 or 2 alkenyl groups in one molecule. Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and other alkenyl groups usually having about 2 to 8 carbon atoms. The alkenyl group may be bonded to a silicon atom at a molecular chain terminal or to a silicon atom at a non-terminal molecular chain (midway in the molecular chain), and preferably contains at least an alkenyl group bonded to a silicon atom at (both) molecular chain terminals. In this case, the alkenyl group may be present only at both molecular chain terminals, or may be present at both molecular chain terminals and at a non-terminal molecular chain (midway in the molecular chain).

[0115] Examples of such alkenyl group-containing diorganopolysiloxanes include linear diorganopolysiloxanes represented by the following general formula (1).

[0116] [Chemistry 1]

[0117]

[0118] (Where R 1 Independently, it is an unsubstituted or substituted monovalent hydrocarbon group without aliphatic unsaturated bonds. X is an alkenyl group, and contains at least one in the molecule. n is an integer greater than 0, m is an integer greater than 0, and a is an integer of 0 to 3 for each bonded silicon atom.)

[0119] In the formula, as R 1An unsubstituted or substituted monovalent hydrocarbon group without aliphatic unsaturated bonds, for example, a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specifically, examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, biphenyl; aralkyl groups such as benzyl, phenylethyl, phenylpropyl, methylbenzyl; and groups in which a part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, and cyano groups, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc. Preferred are unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl, and unsubstituted or substituted phenyl groups such as phenyl, chlorophenyl, fluorophenyl. As R 1 , preferably methyl and phenyl.

[0120] In the formula, as the alkenyl group of X, for example, alkenyl groups having about 2 to 8 carbon atoms such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl can be cited, and among them, lower alkenyl groups such as vinyl and allyl are preferred.

[0121] In the formula, n is an integer of 0 or more, preferably an integer of 10 to 2000, more preferably an integer of 50 to 1200, and m is an integer of 0 or more, preferably an integer of 0 to 40, more preferably an integer of 0 to 20. In addition, n and m are preferably integers satisfying 10 ≤ n + m ≤ 2000, more preferably integers satisfying 50 ≤ n + m ≤ 1200 and 0 ≤ m / (n + m) ≤ 0.2. In this case, the respective units within the parentheses enclosed by n and m can be randomly arranged.

[0122] In the formula, a is an integer of 0 to 3 for each bonded silicon atom, preferably an integer of 1 to 3.

[0123] In addition, the viscosity of such an alkenyl-containing diorganopolysiloxane at 23°C is preferably 10 to 1000000 mPa·s, particularly preferably about 100 to 500000 mPa·s.

[0124] In the present invention, the number of repetitions (or degree of polymerization) of the diorganosiloxane units in the molecule can generally be obtained as the number-average molecular weight (or number-average degree of polymerization) in terms of polystyrene in gel permeation chromatography (GPC) analysis using a solvent such as toluene for elution. In addition, the viscosity can generally be measured using a rotational viscometer (such as BL type, BH type, BS type, cone-plate type, rheometer, etc.) at 23°C.

[0125] (A) The alkenyl-containing diorganopolysiloxane of the component can be used alone or in combination of two or more. In addition, in order not to impair the function of the platinum catalyst mixture of the component (C) described later, before compounding in the composition, the amount of oxygen and moisture contained in the alkenyl-containing diorganopolysiloxane of the component (A) can be reduced in advance. For example, methods such as replacement with an inert gas such as nitrogen, heating, decompression, or a combination thereof can be used.

[0126] [(B) Organohydrogenpolysiloxane]

[0127] (B) The organohydrogenpolysiloxane of the component is an organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and has a linear, cyclic, branched or three-dimensional network structure, and functions as a curing agent (crosslinking agent) for the addition-curable liquid silicone composition to be preserved in the present invention.

[0128] (B) The organohydrogenpolysiloxane of the component functions as a curing agent (crosslinking agent) for the composition to be preserved in the present invention, contains at least two (usually 2 to 200), preferably about 3 to 100 hydrogen atoms (i.e., SiH groups) bonded to silicon atoms in one molecule, and can have a linear, branched, cyclic, or three-dimensional network structure (resin structure).

[0129] As such an organohydrogenpolysiloxane, for example, the organohydrogenpolysiloxane represented by the following average composition formula (2) can be cited.

[0130] H b R 2 c SiO (4-b-c) / 2 (2)

[0131] (In the formula, R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and b and c are numbers such that 0.001 ≤ b ≤ 1.2, 0.8 ≤ c ≤ 2, and 0.8 < b + c ≤ 3, and are preferably numbers such that 0.05 ≤ b ≤ 1, 1.5 ≤ c ≤ 2, and 1.8 ≤ b + c ≤ 2.7.)

[0132] In the formula, as the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond of R 2 , groups similar to the groups exemplified as R 1 in the above general formula (1) can be cited. For example, monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms can be cited, and lower alkyl groups having 1 to 3 carbon atoms such as methyl, phenyl, and 3,3,3-trifluoropropyl are particularly preferred.

[0133] As the component (B), an organohydrogenpolysiloxane which is liquid at room temperature and has 2 to 300, particularly 2 to 150, especially about 2 to 100 silicon atoms in one molecule is preferably used. Further, the hydrogen atoms bonded to the silicon atoms may be located at either the ends of the molecular chain or in the middle (non-end) of the molecular chain, or at both.

[0134] Examples of such organohydrogenpolysiloxanes include methylhydrogencyclosiloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane; tris(dimethylhydro-silyloxy)methylsilane, tris(dimethylhydro-silyloxy)phenylsilane; methylhydrogenpolysiloxane capped with trimethylsilyloxy groups at both ends of the molecular chain; dimethylsiloxane-methylhydrogensiloxane copolymer capped with trimethylsilyloxy groups at both ends of the molecular chain; diphenylsiloxane-methylhydrogensiloxane copolymer capped with trimethylsilyloxy groups at both ends of the molecular chain; methylphenylsiloxane-methylhydrogensiloxane copolymer capped with trimethylsilyloxy groups at both ends of the molecular chain; dimethylsiloxane-diphenylsiloxane-methylhydrogensiloxane copolymer capped with trimethylsilyloxy groups at both ends of the molecular chain; dimethylpolysiloxane capped with dimethylhydro-silyloxy groups at both ends of the molecular chain; methylhydrogenpolysiloxane capped with dimethylhydro-silyloxy groups at both ends of the molecular chain; dimethylsiloxane-methylhydrogensiloxane copolymer capped with dimethylhydro-silyloxy groups at both ends of the molecular chain; diphenylsiloxane-methylhydrogensiloxane copolymer capped with dimethylhydro-silyloxy groups at both ends of the molecular chain; methylphenylsiloxane-methylhydrogensiloxane copolymer capped with dimethylhydro-silyloxy groups at both ends of the molecular chain; dimethylsiloxane-diphenylsiloxane-methylhydrogensiloxane copolymer capped with dimethylhydro-silyloxy groups at both ends of the molecular chain; an organosilicon resin having a three-dimensional network structure composed of dimethylhydro-silyloxy units and SiO 4 / 2 units and optionally containing trimethylsilyloxy units, dimethylsiloxane units, methylhydrogensiloxane units, hydrogen silsesquioxane units and / or methylsilsesquioxane units; compounds in which a part or all of the methyl groups in the above exemplified compounds are replaced with other alkyl groups or phenyl groups, etc. Further, the component (B) may be the same as the organosilicon compound in the component (C) described later.

[0135] The organohydrogenpolysiloxane used in the addition-curable liquid organosilicon composition to be preserved in the present invention can be obtained by a known method. For example, at least one chlorosilane selected from the general formula: R 2 SiHCl2 and R 2 2SiHCl (wherein R 2 is the same as above) can be co-hydrolyzed, or the chlorosilane can be reacted with at least one selected from the general formula: R 2 3SiCl and R2 2SiCl2, where R 2 is the same as above). The organohydrogenpolysiloxane can be a product obtained by equilibration of the polysiloxane obtained by such cohydrolysis. From the viewpoint of curing to form a good silicone rubber or gel, the compounding amount of the organohydrogenpolysiloxane of component (B) is preferably such that the hydrogen atoms bonded to silicon atoms (i.e., SiH groups) in the organohydrogenpolysiloxane of component (B) are 0.5 to 4 moles, preferably 0.8 to 2.5 moles, per mole of the alkenyl group in the alkenyl-containing diorganopolysiloxane of component (A).

[0136] As the organohydrogenpolysiloxane of component (B), one kind can be used alone, or two or more kinds can be used in combination. In addition, in order not to impair the function of the aerobic platinum catalyst mixture of component (C) described later, before compounding in the composition, the amount of oxygen and moisture contained in the organohydrogenpolysiloxane of component (B) can be reduced in advance. For example, methods such as replacement with an inert gas such as nitrogen, heating, depressurization, or a combination thereof can be used.

[0137] [(C) Platinum catalyst]

[0138] The addition-curable liquid silicone composition to be preserved in the present invention is characterized in that, as the (C) component platinum catalyst for promoting the hydrosilylation addition reaction of the alkenyl group in the above-mentioned (A) component and the hydrogen atom (SiH group) bonded to the silicon atom in the above-mentioned (B) component, an aerobic (aerobic reactive) platinum catalyst (a platinum catalyst that is inactive under a closed state blocking contact with the atmosphere (under a closed state of low moisture and low oxidation) and is activated by contact with the atmosphere) is compounded. Further, as a specific example of the (C) component, all of the platinum catalyst mixtures contained in the curable liquid silicone composition disclosed in Patent Document 7 can be cited. Specifically, as described below.

[0139] [Platinum catalyst mixture]

[0140] The platinum catalyst mixture used in the (C) component is an aerobic catalyst composed of a reaction mixture of a platinum-alkenyl-containing organosiloxane complex and an organosilicon compound having at least one SiH group in the molecule, and the amount of the organosilicon compound is such that the hydrogen atoms bonded to silicon atoms (SiH groups) are in an excess molar amount (as a molar ratio, exceeding 1) relative to the alkenyl group in the platinum-alkenyl-containing organosiloxane complex.

[0141] Among them, in the above platinum catalyst mixture, as the platinum-vinyl group-containing organosiloxane complex, preferably, complexes of platinum, platinum chloride, chloroplatinic acid or chloroplatinate with a vinyl group-containing siloxane (such as an organic disiloxane compound having two vinyl groups in the molecule like 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, etc.) can be cited. For example, in the case of the complex of chloroplatinic acid (H2PtCl6) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 3 molecules of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as a bidentate ligand are coordinated to 1 molecule of chloroplatinic acid.

[0142] The platinum-vinyl group-containing organosiloxane complex is preferably dissolved and used in solvents such as toluene, lower alcohols, higher alcohols, and organosilicon systems. The content (concentration) of platinum atoms in the solution at this time is preferably 0.05 to 5% by mass.

[0143] In the above platinum catalyst mixture, as the organosilicon compound having at least one hydrogen atom bonded to a silicon atom (SiH group), an organohydrogensilane, an organohydrogensiloxane oligomer, etc. having at least one (e.g., 1 to 10, preferably 1 to 5) SiH group in the molecule can be preferably used. From the aspects of handleability and safety, an organohydrogensiloxane oligomer is more preferred, and an organohydrogensiloxane oligomer having at least two hydrogen atoms each bonded to a silicon atom (adjacent SiH groups) is further preferred, and the silicon atoms are adjacent to each other through an ether oxygen atom forming a siloxane bond (Si-O-Si). As the molecular structure of this organohydrogensiloxane oligomer, it can be linear or cyclic, and the number of silicon atoms in 1 molecule is preferably 2 to 40, more preferably 2 to 10, and further preferably 2 to 5.

[0144] Examples of the organohydrogensilane and organohydrogensiloxane oligomer used herein include trialkoxy(hydro)silane, alkyldialkoxy(hydro)silane, dialkylalkoxy(hydro)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, etc., and as long as it is one or more selected from these exemplified compounds.

[0145] Regarding the above platinum catalyst mixture, during the preparation of the mixture, the alkenyl group in the platinum-containing alkenyl organosiloxane complex reacts with the SiH group from the above organosilicon compound added in an excess molar amount relative to the alkenyl group (i.e., greater than 1 mole, preferably 1.1 to 30 moles, more preferably 1.5 to 25 moles, further preferably about 5 to 25 moles relative to 1 mole of the alkenyl group) in an oxygen-free atmosphere, resulting in a reaction mixture in a state where all of the alkenyl groups have been converted to alkylene groups by hydrosilylation addition reaction (the alkenyl groups have substantially disappeared) and the SiH groups from the organosilicon compound remaining in the mixture are present.

[0146] In addition, it is worth mentioning that in the above platinum catalyst mixture, when the above organosilicon compound having at least one hydrogen atom bonded to a silicon atom is an organohydrogensiloxane oligomer having at least two hydrogen atoms (hereinafter sometimes referred to as adjacent SiH groups) each bonded to adjacent silicon atoms (hereinafter sometimes referred to as adjacent silicon atoms) mediated by ether oxygen atoms forming a siloxane bond (Si-O-Si) in the molecule (for example, when the above organosilicon compound is 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5,7,7,7-octamethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, etc.), it is preferred to further subject the reaction mixture obtained by uniformly mixing the organohydrogensiloxane oligomer having at least two adjacent SiH groups and the platinum-containing alkenyl organosiloxane complex in an oxygen-free atmosphere to contact with moisture and / or oxygen by means such as mixing in the atmosphere, or to mix the organohydrogensiloxane oligomer having at least two adjacent SiH groups and the platinum-containing alkenyl organosiloxane complex in a state of contact with moisture and / or oxygen at a mixing ratio such that the SiH groups in the organohydrogensiloxane oligomer having at least two adjacent SiH groups are in an excess molar amount relative to the alkenyl groups in the platinum-containing alkenyl organosiloxane complex, thereby obtaining a reaction mixture thereof. Thus, the addition-curing type liquid organosilicon composition containing this mixture as a hydrosilylation addition reaction catalyst can further improve the long-term one-component storage stability under closed conditions without impairing the curability when in contact with moisture (humidity) and / or oxygen in the atmosphere.

[0147] The method for preparing the above platinum catalyst mixture is characterized in that the platinum-containing alkenyl organosiloxane complex and the above organosilicon compound having at least one hydrogen atom bonded to a silicon atom (SiH group) are mixed in an oxygen-free atmosphere (for example, under an anaerobic and low moisture amount closed state where contact with moisture (humidity) and oxygen is blocked) at a mixing ratio such that the SiH groups of the organosilicon compound are in an excess molar amount relative to the alkenyl groups in the platinum-containing alkenyl organosiloxane complex, thereby obtaining a reaction mixture thereof.

[0148] Among them, the compounding ratio in which the SiH group of the organosilicon compound is in an excessive molar amount relative to the alkenyl group in the platinum-containing alkenyl group-containing organosiloxane complex means the relationship between the compounding amounts of the platinum-containing alkenyl group-containing organosiloxane complex and the organosilicon compound, such that relative to 1 mole of the alkenyl group in the complex, the SiH group in the organosilicon compound is greater than 1 mole, preferably 1.1 to 30 moles, more preferably 1.5 to 25 moles, and further preferably about 5 to 25 moles.

[0149] In addition, the mixing method is not particularly limited as long as it is a method of uniformly mixing the platinum-containing alkenyl group-containing organosiloxane complex and the above-mentioned organosilicon compound having at least one hydrogen atom bonded to a silicon atom (SiH group) in the molecule. For example, it is preferably carried out using a glass reactor such as a glass flask or a stainless-steel reactor.

[0150] The atmosphere during mixing does not contain oxygen, and is preferably an inert gas atmosphere such as nitrogen or under reduced pressure (vacuum). The temperature at this time does not need to be heated and can be room temperature (23 °C ± 15 °C, the same below). In addition, the mixing time at this time (i.e., the reaction time) only needs to be a time for uniformly mixing the platinum-containing alkenyl group-containing organosiloxane complex and the organosilicon compound. For example, it is preferably 0.5 to 100 hours, and particularly preferably 1 to 24 hours.

[0151] As a method for preparing the above platinum catalyst mixture, in the above platinum catalyst mixture, when the above-mentioned organosilicon compound having at least one hydrogen atom bonded to a silicon atom is an organohydrogensiloxane oligomer having at least two hydrogen atoms each bonded to silicon atoms adjacent to each other via ether oxygen atoms forming a siloxane bond (Si-O-Si) (for example, when the above organosilicon compound is 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5,7,7,7-octamethyletetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, etc.), it preferably includes a step of further mixing the reaction mixture obtained by mixing in the above oxygen-free atmosphere in a state of contact with moisture and / or oxygen. This step uses means such as mixing in the atmosphere to bring the reaction mixture into contact with moisture and / or oxygen. For example, the mixing time in the atmosphere is preferably 0.5 to 100 hours, and particularly preferably 1 to 12 hours. Then, the platinum catalyst mixture is stored in a sealed container.

[0152] Furthermore, as another method for preparing a platinum catalyst mixture, it is a method for preparing a platinum catalyst mixture by mixing a platinum-containing alkenyl organosiloxane complex with an organosilicon compound having at least one hydrogen atom bonded to a silicon atom (SiH group) in the molecule to obtain the reaction mixture. It is characterized in that the above-mentioned 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) each bonded to silicon atoms adjacent to each other via an oxygen atom forming a siloxane bond (Si-O-Si), and the platinum-containing alkenyl organosiloxane complex is mixed with the above-mentioned organosilicon compound having at least one hydrogen atom bonded to a silicon atom (SiH group) in a mixing ratio such that the SiH groups of the organosilicon compound are in an excess molar amount relative to the alkenyl groups in the platinum-containing alkenyl organosiloxane complex, in a state of contact with moisture and / or oxygen. By mixing the above components in the atmosphere and other means using this preparation method, and contacting with moisture and / or oxygen, for example, the mixing time in the atmosphere is preferably 0.5 to 100 hours, particularly preferably 1 to 12 hours. Then, the platinum catalyst mixture is stored in a sealed container.

[0153] Thus, the addition-curing type liquid organosilicon composition containing this mixture as a hydrosilylation addition reaction catalyst can further improve the long-term one-component storage stability under sealing without impairing the curability when contacting with moisture (humidity) and / or oxygen in the atmosphere.

[0154] According to the platinum catalyst mixture obtained as described above, the platinum catalyst mixture is in a state with low catalytic activity as a hydrosilylation addition reaction catalyst in a sealed container blocking contact with oxygen and having a low moisture content, but becomes a state with high catalytic activity when contacting with moisture (humidity) and / or oxygen in the atmosphere. Therefore, for example, if this platinum catalyst mixture is added as a curing catalyst to a curing type liquid organosilicon composition by hydrosilylation addition reaction, when the curing type liquid organosilicon composition is stored and kept in a sealed container blocking contact with oxygen and having a low moisture content, the composition can exhibit sufficient long-term one-component storage stability from refrigeration to room temperature. On the other hand, if the sealed container is opened and the composition is contacted with moisture (humidity) and / or oxygen in the atmosphere, etc., the platinum catalyst mixture in the composition is activated at room temperature and becomes a state with high catalytic activity. In this curing type liquid organosilicon composition, even without heating, the crosslinking (curing) reaction by hydrosilylation addition reaction proceeds rapidly, and not only the air contact surface but also the deep part cures rapidly, enabling the curing type liquid organosilicon composition to be rubberized and gelled.

[0155] In the addition-curing type liquid silicone composition which is the preservation object of the present invention, the compounding amount of the platinum catalyst mixture of component (C) may be a so-called catalytic amount, which is 0.1 to 1000 ppm, preferably 0.5 to 200 ppm, in terms of the mass of platinum atoms contained in component (C), relative to the total mass of components (A) and (B). If the compounding amount of component (C) is less than the above range, when using the material, the curing of the material becomes insufficient due to the influence of catalyst hindrance factors. If it is more than the above range, the storage stability becomes poor. It should be noted that since the compounding amount of component (C) is a so-called catalytic amount, the excess molar fraction of SiH groups remaining in component (C) is a very small amount that can be ignored, and it basically does not affect the value of the molar ratio of SiH groups in the above-mentioned component (B) to alkenyl groups in component (A).

[0156] [Other components]

[0157] In the addition-curing type liquid silicone composition which is the preservation object of the present invention, in addition to the above components (A) to (C), various optional components described below can be added as needed within the range that does not impair the performance of the addition-curing type liquid silicone composition.

[0158] [(D) Dehydrating agent]

[0159] In the addition-curing type liquid silicone composition which is the preservation object of the present invention, furthermore, as an optional component, as needed, a dehydrating agent of component (D) can be compounded in order to remove moisture in the composition. By compounding the dehydrating agent of component (D), more excellent storage stability can be obtained.

[0160] As described above, the platinum catalyst mixture of component (C) as the basic technology of the addition-curing type liquid silicone composition has the property of suppressing the catalytic activity low in an anaerobic and low-moisture environment where contact with moisture (moisture) and oxygen is blocked, and activating the catalytic function by moisture and / or oxygen from the external atmosphere (atmosphere) etc. (oxygen-required reaction type). Therefore, it is confirmed that by reducing the moisture content in each component and the moisture content in the mixed composition, the one-component storage stability of the addition-curing type liquid silicone composition is improved, and introducing a structure that consumes (dehydrates) moisture from the components and trace moisture invading from outside the container in the composition in the state of being stored in a sealed container is useful for ensuring the one-component storage stability.

[0161] The compound capable of performing this dehydration can be an inorganic compound or an organic compound as long as it does not impair the functions of the above components (A), (B), and (C). Depending on the compound capable of dehydration, foaming sometimes occurs due to the compound by-produced by the dehydration reaction, and in addition, the decomposition of the hydrosiloxane in the composition and the reduction of the catalytic activity of the platinum catalyst mixture often occur.

[0162] Therefore, as the dehydrating agent of component (D), which is a dehydrating agent capable of efficiently dehydrating the system, silyl ketenes (including silyl ketene acetals), silyl enol esters, and α-silyl esters are preferred. These compounds have structures in which the by-products during dehydration do not impair the functions of the above-mentioned components (A), (B), and (C), and are soluble in the addition-curable liquid silicone composition, so that a stable curable liquid silicone composition can be prepared. Among them, silyl ketenes (including silyl ketene acetals) and α-silyl esters undergo dehydration reactions under non-basic conditions, so they do not cause the decomposition of hydrosiloxanes and the reduction of the catalytic activity of the platinum catalyst mixture.

[0163] Examples of silyl ketenes (including silyl ketene acetals) include 1-methoxy-2-methyl-1-(trimethylsilyloxy)propene, dimethyl ketene trimethylsilyl acetal, tert-butoxy-1-(trimethylsilyloxy)propene, etc.

[0164] Examples of α-silyl esters include ethyl 2-(trimethoxysilyl)propionate (ECMS), octyl 2-(methyldimethoxysilyl)propionate (OCMS-2), etc.

[0165] The dehydrating agent of component (D) can be added in advance among the various components, can be added during the preparation of the composition, or can be added later to the prepared composition. In addition, its addition amount is preferably 5% by mass or less of the total composition, and particularly preferably 2% by mass or less.

[0166] In addition, a catalyst for promoting the reaction between component (D) and water can be added. Examples of such catalysts include titanates (tetrakis(isopropyl) titanate (TPT), tetrabutyl titanate (TBT), tetrakis(2-ethylhexyl) titanate (TOT), etc.), titanium chelate compounds (diisopropoxybis(ethyl acetoacetate)titanium, titanium tetraacetylacetonate, etc.), tin compounds (dibutyl dimethoxysilane, dibutyltin dilaurate, etc.), etc. Its addition amount is preferably 2% by mass or less of the whole composition, and particularly preferably 1% by mass or less.

[0167] [(E) Addition reaction controller]

[0168] In the addition-curable liquid silicone composition to be preserved according to the present invention, furthermore, as needed, for the same purpose of improving the one-component storage stability as the dehydrating agent of the above-mentioned component (D), an addition reaction controller of component (E) is compounded as an optional component, which is also useful.

[0169] As described above, the platinum catalyst mixture as the component (C), which is the basic technology of the addition-curing type liquid silicone composition, has the property of activating the catalytic function by moisture. Therefore, sometimes due to the moisture in each component, the moisture mixed in the process of preparing the composition or filling the container, and the moisture invading from outside the closed container, a part of the platinum catalyst mixture of the component (C) is activated as an addition reaction catalyst. Due to this part of the activated catalyst, the one-component storage stability of the composition may be significantly reduced. By additionally blending the addition reaction controller of the component (E), it is possible to suppress such a reduction in the one-component storage stability.

[0170] Examples of the addition reaction controller as the component (E) include compounds selected from acetylenic alcohols such as 1-ethynylcyclohexanol and 3-methyltridec-1-yn-3-ol (EMDC), silanes, siloxane-modified products of acetylenic alcohols such as dimethylbis(1,1-dimethyl-2-propionyloxy)silane (PLR-22) and 3-(trimethylsilyloxy)-3-methyl-1-butyne (PLR-31), phosphite compounds (especially phosphite esters) such as tris(isopropyl)phosphite, tris(di-tert-butylphenyl)phosphite, triphenylphosphite, and tris(2-ethylhexyl)phosphite, ethylenediamines such as tetramethylethylenediamine, benzotriazoles such as benzotriazole and 5-methyl-1H-benzotriazole, and mixtures thereof. Among them, phosphite compounds, especially tris(isopropyl)phosphite and tris(di-tert-butylphenyl)phosphite among phosphite esters, are preferred because an addition-curing type liquid silicone composition having good one-component storage stability in a closed state can be obtained.

[0171] The addition amount of the addition reaction controller of the component (E) can be any addition amount within the range that does not affect the curability of the addition-curing type liquid silicone composition according to the performance of each addition reaction controller. In the case of phosphite compounds such as phosphite esters, the addition amount can be a trace amount, and can be an amount of less than 1 mole, especially about 0 to 0.75 mole, relative to 1 mole of platinum atoms contained in the composition. If the addition amount of the component (E) is too large, the platinum catalyst mixture of the component (C) activated by moisture will be deactivated during use, so the curability in the open air may be reduced.

[0172] [(F) Inorganic filler]

[0173] In the addition-curable liquid silicone composition to be preserved according to the present invention, in order to adjust the viscosity before curing, improve the strength of the cured silicone rubber or silicone gel, and adjust the appearance color, an inorganic filler as the component (F) can be compounded as an optional component as needed. As the inorganic filler of the component (F), for example, reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide can be added; non-reinforcing inorganic fillers such as calcium silicate, titanium dioxide, iron oxide, and carbon black.

[0174] Regarding the compounding amount of the inorganic filler of the component (F), generally, it is 200 parts by mass or less relative to 100 parts by mass of the component (A). When the component (F) is compounded, relative to 100 parts by mass of the component (A), it is preferably 0.1 to 200 parts by mass, more preferably 0.5 to 50 parts by mass. If the amount of the inorganic filler used is less than 0.1 part by mass, the addition effect may not be obtained. If it exceeds 200 parts by mass, it may be difficult to uniformly mix as a mixture.

[0175] [(G) Adhesion promoter]

[0176] In the addition-curable liquid silicone composition to be preserved according to the present invention, in the case of applications requiring high self-adhesion, furthermore, as an optional component, as needed, in order to improve the adhesion of the cured product to various substrates, for example, a hydrolyzable organosilane compound such as an alkoxysilane containing a monovalent hydrocarbon group (so-called carbon-functional silane or silane coupling agent) and / or its partial hydrolysis condensate can be compounded as the adhesion promoter of the component (G), and the monovalent hydrocarbon group has a functional group containing a heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom (epoxy group, (meth)acryloyloxy group, mercapto group, etc.).

[0177] When the adhesion promoter of the component (G) is compounded, its compounding amount is preferably 0.1 to 20 parts by mass, more preferably about 0.2 to 10 parts by mass relative to 100 parts by mass of the component (A). If the compounding amount of the adhesion promoter is less than 0.1 part by mass, the target adhesion may not be sufficiently exhibited. If it exceeds 20 parts by mass, the viscosity of the material may extremely decrease sometimes.

[0178] [(H) Plasticizer]

[0179] In the addition-curing type liquid silicone composition which is the object to be preserved in the present invention, as an optional component, for adjusting the viscosity of the composition and the hardness of the cured product as needed, as the plasticizer of the component (H), it can be compounded with dimethylpolysiloxane (dimethyl silicone oil) capped with trimethylsilyl groups at both ends of the molecular chain, dimethylsiloxane-diphenylsiloxane copolymer capped with trimethylsilyl groups at both ends of the molecular chain, dimethylsiloxane-methylphenylsiloxane copolymer capped with trimethylsilyl groups at both ends of the molecular chain (methylphenyl silicone oil), etc., so-called non-functional silicone oils which do not contain functional groups such as alkenyl groups and hydrosilyl groups (SiH groups) participating in the hydrosilylation addition reaction in the molecule.

[0180] When compounding the plasticizer of the component (H), its compounding amount is preferably 0.1 to 50 parts by mass, more preferably about 0.5 to 20 parts by mass, based on 100 parts by mass of the component (A). If the compounding amount of the non-functional silicone oil (plasticizer) is less than 0.1 part by mass, plasticization for the purpose of addition may sometimes not be achieved. If it is more than 50 parts by mass, the plasticizer may sometimes separate and exude from the cured material.

[0181] In the addition-curing type liquid silicone composition which is the object to be preserved in the present invention, in addition to the above-mentioned dehydrating agent (D), addition reaction control agent (E), inorganic filler (F), adhesion-imparting agent (G) and plasticizer (H) as optional components, as needed, it is possible to further compound pigment pastes using the same components as the non-functional silicone oil as the plasticizer and additives such as reinforcing silicone resins as other optional components.

[0182] (Preparation method of addition-curing type liquid silicone composition)

[0183] When preparing the addition-curing type liquid silicone composition which is the object to be preserved in the present invention, in an environment with a low oxygen concentration (substantially oxygen-free) and a low moisture content (for example, under a nitrogen atmosphere) at room temperature, while blocking contact with moisture (humidity) and oxygen, it is advisable to add the above-mentioned respective components in the order of (A) alkenyl-containing diorganopolysiloxane, (B) organohydrogenpolysiloxane, dehydrating agent (D) as an optional component, addition reaction control agent (E), inorganic filler (F), adhesion-imparting agent (G) and plasticizer (H), and (C) aerobic platinum catalyst mixture while mixing. It should be noted that in the case of components not to be added, skip their order and continue adding the subsequent components.

[0184] (Manufacturing method of container for storing addition-curing type liquid silicone composition)

[0185] The container for storing the addition-curing type liquid silicone composition of the present invention can be manufactured by the following steps.

[0186] (i) The prepared addition-curable liquid silicone composition is filled into the container constituting the first sealing structure from the injection port of the container under the same environment as when it was prepared (at room temperature, in an environment of low oxygen concentration (substantially oxygen-free) and low moisture content that blocks contact with moisture (humidity) and oxygen). A lid made of metal, glass, ceramic, or resin is inserted, fitted, or screwed into the injection port, or the injection port itself is bonded or welded (heat-welded) to seal the injection port, thereby forming the first sealing structure.

[0187] (ii) A member having a function of consuming and removing oxygen and moisture (a dehydrating and deoxidizing agent, or a combination of a dehydrating agent and a deoxidizing agent) is provided at or near the sealed portion of the first sealing structure.

[0188] (iii) The first sealing structure is at least entirely covered with a second sealing structure, or the entire first sealing structure is covered, and further, the sealed portion and the member having a function of consuming and removing oxygen and moisture are sealed. Specifically, by fixing a film-like second sealing structure to the outer peripheral portion of the sealed portion of the first sealing structure using an adhesive or heat-welding, the first sealing structure is at least entirely covered and sealed. Alternatively, after the entire first sealing structure is housed inside a bag-like second sealing structure, the opening of the second sealing structure is sealed by heat-welding or bonding, thereby covering and sealing the entire first sealing structure.

[0189] By the above procedures, a container for storing the addition-curable liquid silicone composition of the present invention is obtained.

[0190] (Curing method of addition-curable liquid silicone composition)

[0191] The curing method of the addition-curable liquid silicone composition as the object to be stored in the present invention is characterized by including the following steps: taking out the addition-curable liquid silicone composition from the above-mentioned storage container and exposing it to the atmosphere at room temperature to cure it.

[0192] Here, if the addition-curable liquid silicone composition is exposed to the atmosphere, moisture (humidity) and / or oxygen in the atmosphere come into contact with the platinum catalyst mixture in the composition, activating the catalytic function of the platinum catalyst mixture. Even at room temperature, the curing of the addition-curable liquid silicone composition starts. At this time, not only the air-contact surface of the composition but also the deep part cures rapidly, and a silicone rubber cured product or a silicone gel cured product can be formed.

[0193] The cured products of the above addition-curable liquid silicone composition, namely silicone rubber and silicone gel, have excellent heat resistance and electrical insulation properties and can be applied to in-vehicle components, aircraft, household electrical appliances, etc.

[0194] Examples

[0195] Examples and comparative examples are shown below for a more specific description of the present invention, but the present invention is not limited by the following examples. It should be noted that the viscosity is the measured value using a rotational viscometer at 23°C, and the degree of polymerization represents the number-average degree of polymerization in terms of polystyrene in GPC analysis using toluene as an elution solvent. In addition, Me represents methyl and Vi represents vinyl. "Room temperature" means 23°C. The oxygen concentration in "air" is 21 vol% and the humidity is 50% RH.

[0196] (Preparation of platinum catalyst mixture)

[0197] An aerobic platinum catalyst mixture (C-1) was prepared according to the method described in Patent Document 7 (International Publication No. 2022 / 270366) according to the following procedure.

[0198] (Preparation procedure)

[0199] In a nitrogen atmosphere at room temperature (23°C), a toluene solution of (C-a) chloroplatinic acid-1,3-divinyltetramethyldisiloxane complex (platinum atom content 0.5 mass%) as a platinum-containing alkenyl organosiloxane complex and (C-b) 1,1,3,3-tetramethyldisiloxane as an organohydrogenpolysiloxane were uniformly mixed in a 25 g glass bottle for 12 hours, reacted, and then sealed. Further, the lid of the glass bottle was opened in the air at room temperature (23°C), and the mixture was uniformly mixed while further contacting the mixture with the air for 2 hours, and then sealed, thereby preparing an aerobic platinum catalyst mixture (C-1).

[0200] [Table 1]

[0201]

[0202] Using the above-prepared platinum catalyst mixture (C-1), addition-curable liquid silicone compositions (S-1) to (S-4) were prepared according to the following procedure.

[0203] (Preparation of curable liquid silicone composition)

[0204] In a nitrogen atmosphere at room temperature (23°C), the respective components were uniformly mixed in a glass bottle in the blending amounts shown in Table 2 below, and sealed in the glass bottle, thereby preparing each composition. Further, in Table 2, the molar ratio of the SiH group in component (B) to the vinyl group in component (A) for the compositions (S-1) to (S-4) is 2.2.

[0205] For the addition at this time, the components are added while mixing in the order of (A) an alkenyl-containing diorganopolysiloxane, (B) an organohydrogenpolysiloxane, (D) a dehydrating agent, (E) an addition reaction controller, and (C) an air-requiring platinum catalyst mixture. It should be noted that in the case of components not to be added, their order is skipped and the addition of subsequent components is continued.

[0206] In addition, in order to prepare the composition with good reproducibility, the (A) alkenyl-containing diorganopolysiloxane and (B) organohydrogenpolysiloxane used were products that had been previously subjected to vacuum degassing at 120 °C in a glass flask to dehydrate. In addition, the mixing step / container filling step of the composition was carried out under a nitrogen atmosphere.

[0207] Furthermore, the details of each component are as described below.

[0208] (A) Alkenyl-containing diorganopolysiloxane:

[0209] (A-1) A vinyl-containing linear diorganopolysiloxane having a viscosity of 5000 mPa·s at 23 °C represented by the following average formula

[0210] Vi(Me)2SiO-(Si(Me)2O) 300 -Si(Me)2Vi

[0211] (A-2) A vinyl-containing linear diorganopolysiloxane having a viscosity of 800 mPa·s at 23 °C represented by the following average formula

[0212] Vi(Me)2SiO-(Si(Me)2O) 100 -Si(Me)3

[0213] (A-3) A vinyl-containing branched-chain diorganopolysiloxane having a viscosity of 800 mPa·s at 23 °C represented by the following average formula

[0214] Vi(Me)2SiO-(Si(Me)2O) 98 -(Si(Me)O 3 / 2 )2-Si(Me)3

[0215] (B) Organohydrogenpolysiloxane:

[0216] (B-1) A linear organohydrogenpolysiloxane represented by the following average formula

[0217] (Me)3SiO-(Si(Me)2O) 63 -(Si(H)(Me)O) 20 -Si(Me)3

[0218] (B-2) Linear organohydrogensiloxane represented by the following average formula

[0219] H(Me)2SiO-(Si(Me)2O) 18 -SiH(Me)2

[0220] (C) Aerophilic platinum catalyst mixture:

[0221] The prepared aerophilic platinum catalyst mixture (C-1) was used.

[0222] (D) Dehydrating agent:

[0223] (D-1) Ethyl 2-(trimethylsilyl)propionate (ECMS) (α-silyl esters)

[0224] As (D’), tetra(isopropyl) titanate (TPT) or zirconium(IV) tetraisopropoxide (Zr(O-Pr)4) was added as a catalyst to promote the reaction of component (D) with moisture.

[0225] (E) Addition reaction controller:

[0226] (E-1) Tris(di-tert-butylphenyl) phosphite represented by the following formula (0.31 mass% toluene solution)

[0227] [Chemical formula 2]

[0228]

[0229] In the prepared curable liquid silicone composition, the one-component storage stability under closed conditions, the curability (room temperature curability) after storage under room temperature atmosphere exposure, and the hardness of the cured product were evaluated as described below.

[0230] Regarding the storage stability of a single-component under confinement, a curable liquid silicone composition was filled into a glass bottle under a nitrogen atmosphere and sealed (i.e., after filling 10 g of the composition shown in Table 2 into a glass bottle (outer dimensions: diameter 35 mm, height 65 mm) in nitrogen, a cap (an inner plug of cap type made of polyethylene at the part in contact with the injection port of the glass bottle, and the pressed part is composed of a metal cap (polyethylene inner plug + metal cap)) was fitted (pressed in) at the injection port (opening part) of the glass bottle to form a sealed container (the first sealing structure in the present invention, hereinafter referred to as the glass bottle)), and then, together with the glass bottle, it was placed in the atmosphere / at room temperature, and the thickening and gelling behaviors of the curable liquid silicone composition were observed. At this time, regarding the thickening and gelling behaviors of the curable liquid silicone composition, when the glass bottle was tilted, the degree to which the composition in the glass bottle followed its flow (fluidity) was observed, and the state in which the fluidity became worse compared with that immediately after sealing was judged as thickening or gelling of the curable liquid silicone composition. In addition, at this time, after the glass bottle in which the curable liquid silicone composition was sealed was placed in the atmosphere / at room temperature, it was first observed for 5 minutes, and then, observed every day, and the time (days) until the curable liquid silicone composition thickened or gelled was confirmed.

[0231] Room temperature curability As described above, the curable liquid silicone composition stored in a sealed state in a glass bottle for 1 day was taken out into another container (depth 4 mm) under a nitrogen atmosphere, and in a state where it was exposed to the atmosphere / room temperature environment, the time until it cured into a rubber-like or gel-like state was evaluated as the curing time. Further, at this time, the inside of the container was punctured with a needle to confirm the curing state of the deep part.

[0232] Regarding the hardness of the cured product, the curable liquid silicone rubber composition just prepared above was cast into a glass dish, and in the cured product after being exposed to the atmosphere / room temperature environment for 24 hours, for the rubber-like cured product, the hardness specified in JIS K 6249 (Type A hardness tester) was measured, and for the gel-like cured product, the penetration (consistency of 1 / 4 cone according to JIS K 2220) specified in JIS K 6249 was measured.

[0233] The above results are shown in Table 2.

[0234] [Table 2]

[0235]

[0236] (Production of storage container)

[0237] As the first sealing structure in the present invention, after filling 10 g of the composition shown in Table 2 in a glass bottle (outer dimensions: diameter 35 mm, height 65 mm) in nitrogen, a lid (a cap-shaped inner plug made of polyethylene (outer diameter 28 mm) at the part in contact with the injection port of the glass bottle, and a lid composed of a metal lid at the pressed part (polyethylene inner plug + metal lid)) was fitted (pressed in) to the injection port (opening part, inner diameter 23 mm) of the glass bottle to produce a sealed container (hereinafter referred to as a glass bottle). Next, using the combinations shown in Table 3, storage containers were produced, and the storage stability of the filled composition was evaluated.

[0238] (Example 1)

[0239] The produced glass bottle was stored in a bag made of a polyethylene film (polyethylene bag, thickness 110 μm). After disposing of a dehydration and deoxidation agent (RP series RP-1AN (manufactured by Mitsubishi Gas Chemical Company, Inc.)) 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 sealed by heat welding to seal the glass bottle and the dehydration and deoxidation agent, and a storage container was produced. This sealed polyethylene bag is the second sealing structure. Furthermore, this storage container corresponds to Figure 3 the packaging 30 shown, the glass bottle is the main container 31, the polyethylene bag is the sealing film 32, and the dehydration and deoxidation agent is the member 33.

[0240] (Example 2)

[0241] In Example 1, a bag (aluminum laminated polyethylene bag, thickness 100 μm) formed by laminating an aluminum foil (thickness 10 μm) on the outer side of a polyethylene film (thickness 90 μm) was used instead of the polyethylene bag. Otherwise, a storage container was produced in the same manner as in Example 1. Furthermore, this storage container corresponds to Figure 3 the packaging 30 shown, the glass bottle is the main container 31, the aluminum laminated polyethylene bag is the sealing film 32, and the dehydration and deoxidation agent is the member 33.

[0242] (Comparative Example 1)

[0243] The above glass bottle was directly used as the storage container.

[0244] (Comparative Example 2)

[0245] In Example 1, the dehydration and deoxidation agent was not provided, and otherwise a storage container was produced in the same manner as in Example 1.

[0246] (Comparative Example 3)

[0247] In Example 1, instead of using a dehydration and deoxidizer, a dehydrating agent (Ageless Dry ADN-5 (manufactured by Mitsubishi Gas Chemical Company, Inc.)) having only a water-dehydrating function was used, and a storage container was produced in the same manner as in Example 1 except for this.

[0248] (Comparative Example 4)

[0249] In Example 1, instead of using a dehydration and deoxidizer, a deoxidizing agent (Ageless FJ (manufactured by Mitsubishi Gas Chemical Company, Inc.)) having only a deoxidizing function was used, and a storage container was produced in the same manner as in Example 1 except for this.

[0250] (Comparative Example 5)

[0251] In Example 2, no dehydration and deoxidizer was provided, and a storage container was produced in the same manner as in Example 1 except for this.

[0252] First, as the first sealing structure in the present invention, a container (hereinafter referred to as a box container) was produced in which 250 g of the composition shown in Table 2 was filled in a metal (aluminum) box main body container (outer dimensions: diameter 47 mm, height 215 mm) in nitrogen, and then a lid (plunger (aluminum, outer diameter 46 mm)) was inserted into the injection port (opening part, inner diameter 46 mm) of the box and sealed. Next, storage containers were produced in the combinations shown in Table 3, and the storage stability of the filled composition was evaluated.

[0253] (Example 3)

[0254] After disposing one dehydration and deoxidizer (RP series RP-1AN (manufactured by Mitsubishi Gas Chemical Company, Inc.)) on the plunger of the produced box container, a polyethylene sealing film (polyethylene film) was adhered to the opening end portion of the box main body container into which the plunger was inserted by using an adhesive and fixed, so as to be sealed in such a manner that a lid was placed on the opening part (injection port) of the box main body container. The fixed polyethylene film is the second sealing structure. Further, this storage container corresponds to Figure 2 the box 20 shown, the box main body container is the main body container 21a, the plunger is the plunger 21b, the polyethylene film is the sealing film 22, and the dehydration and deoxidizer is the member 23.

[0255] (Comparative Example 6)

[0256] The above box container was directly used as a storage container.

[0257] (Comparative Example 7)

[0258] In Example 3, no dehydration and deoxidizer was provided, and a storage container was produced in the same manner as in Example 3 except for this.

[0259] [Table 3]

[0260]

[0261] For the storage container produced as described above, the following storage evaluation was carried out.

[0262] Regarding the storage evaluation conditions, the produced storage container was stored in a thermostatic chamber at a temperature of 40 °C and a humidity of 10 - 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 maintained a liquid state. That is, regarding the thickening and gelling behavior of the curable liquid silicone composition, when the main container (glass bottle or box container) was tilted, the degree to which the composition in the main container followed its flow (fluidity) was observed, and the state in which the fluidity became worse compared to just after sealing was judged as thickening or gelling of the curable liquid silicone composition. In addition, at this time, after the storage container in which the curable liquid silicone composition was sealed was stored in the thermostatic chamber, it was observed every 7 days to confirm the time (number of days) until the curable liquid silicone composition thickened or gelled. Further, in the case of sealing a glass bottle with a second sealing structure (polyethylene bag, aluminum laminated polyethylene bag) (Examples 1 and 2, Comparative Examples 2 and 3), and in the case of a main container composed of a metal box main container (Examples 3, Comparative Examples 6 and 7), since the internal state (liquid / gel) could not be determined, multiple samples were prepared, and the storage property was continuously evaluated by opening the sealing form every 7 days.

[0263] Table 4 shows the results of the storage evaluation (evaluation of the storage property (period of maintaining a liquid state) at 40 °C) when the compositions (S-1) to (S-4) were respectively sealed in the above-produced storage containers.

[0264] According to the storage container of the present invention, the addition-curable liquid silicone composition can be stored for a long period of 42 days or more. After the storage, it was confirmed that by contacting with air without heating and opening (at room temperature in the atmosphere), the platinum catalyst mixture was also activated, and the addition reaction proceeded to cure into a rubbery or gel-like state.

[0265] [Table 4]

[0266]

[0267] Explanation of reference numerals

[0268] 1 Addition-curable liquid silicone composition

[0269] 10 Cans

[0270] 11a, 21a, 31, 41 Main container

[0271] 11b Lid part

[0272] 11h opening

[0273] 12, 22, 32, 42 sealing films

[0274] 13, 23, 33, 43 components

[0275] 20 case

[0276] 21b plunger

[0277] 21n nozzle part

[0278] 30, 40 packages

[0279] 32a bag-shaped sealing film with an opening

[0280] 32s, 41s, 42s sealing parts

Claims

1. A container for storing an addition-curing type liquid silicone composition, which is a container for storing an addition-curing type liquid silicone composition, wherein, The addition-curable liquid silicone composition contains a platinum catalyst 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 and is activated by contact with the atmosphere, and is crosslinked and cured by a hydrosilylation addition reaction in the presence of the platinum catalyst activated in the atmosphere. It includes: a first sealing structure that is a container enclosing the addition-curable liquid silicone composition and has a sealing portion formed by sealing an injection port for injecting the addition-curable liquid silicone composition; a second sealing structure that is a film covering at least the entire sealing portion of the first sealing structure or the entire first sealing structure to further seal the sealing portion; and a member provided between the first sealing structure and the second sealing structure and having a function of consuming and removing oxygen and moisture.

2. The container for storing the addition-curable liquid organosilicon composition according to claim 1, wherein, The addition-curable liquid silicone composition contains the following components (A) to (C). (A) A diorganopolysiloxane having at least one alkenyl group in one molecule. (B) An organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: The amount is such that, relative to each 1 mole of alkenyl groups in component (A), the hydrogen atoms bonded to silicon atoms in component (B) are 0.5 to 4 moles. (C) A platinum catalyst mixture activated by oxygen and / or moisture: The amount is such that, in terms of the mass of platinum atoms in component (C) relative to the total mass of components (A) and (B), it is 0.1 to 1000 ppm.

3. The container for storing the addition-curable liquid organosilicon composition according to claim 2, wherein, The platinum catalyst mixture is an aerobic platinum catalyst mixture composed of a reaction mixture of a platinum-alkenyl-containing organosiloxane complex and an organosilicon compound having at least one SiH group in the molecule, and the amount of the organosilicon compound is such that the hydrogen atoms bonded to silicon atoms, i.e., SiH groups, are in an excess molar amount relative to the alkenyl groups in the platinum-alkenyl-containing organosiloxane complex.

4. The container for storing the addition-curable liquid organosilicon composition according to claim 3, wherein, The platinum-alkenyl-containing organosiloxane complex is a complex of platinum, platinum chloride, chloroplatinic acid, or chloroplatinate and a vinyl-containing siloxane.

5. The container for storing the addition-curing type liquid silicone composition according to claim 4, wherein, The vinyl-containing siloxane is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

6. The container for storing the addition-curable liquid organosilicon composition according to claim 3, wherein, The organosilicon compound having at least one hydrogen atom bonded to a silicon atom is an organohydrogensilane or an organohydrogensiloxane oligomer.

7. The container for storing the addition-curable liquid organosilicon composition according to claim 3, wherein, The organosilicon compound having at least one hydrogen atom bonded to a silicon atom is one or more selected from trialkoxy(hydro)silanes, alkyldialkoxy(hydro)silanes, dialkylalkoxy(hydro)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.

8. The container for storing the addition-curable liquid organosilicon composition according to claim 3, wherein, The organosilicon compound having at least one hydrogen atom bonded to a silicon atom is an organohydrogensiloxane oligomer having at least two hydrogen atoms each bonded to a silicon atom, i.e., SiH groups, in the molecule, and the silicon atoms are adjacent to each other through oxygen atoms forming siloxane bonds Si-O-Si.

9. The container for storing the addition-curable liquid organosilicon composition according to claim 1, wherein, The first sealing structure is composed of a container made of metal, glass, ceramic or resin, and the sealing part is a sealing part formed by inserting, fitting or screwing a lid made of metal, glass, ceramic or resin into the injection port into which the addition-curable liquid organosilicon composition is injected, or by bonding or welding the injection port itself to seal the injection port.

10. The container for storing the addition-curable liquid organosilicon composition according to claim 1, wherein, The second sealing structure includes a resin film.

11. The container for storing the addition-curable liquid organosilicon composition according to claim 1, wherein, The second sealing structure includes a laminated structure film of a resin layer and a metal layer or a laminated structure film of a metal foil and a metal layer.

12. The container for storing the addition-curing type liquid organosilicon composition according to claim 1, wherein, The second sealing structure is heat-sealed or bonded to the outer peripheral part of the sealing part of the first sealing structure in a state of covering at least the whole sealing part of the first sealing structure to further seal the sealing part.

13. The container for storing the addition-curable liquid organosilicon composition according to claim 1, wherein, In a state where the second sealing structure covers all of the first sealing structure, the second sealing structure is hermetically sealed by heat-sealing or bonding to further seal the sealing part.

14. The container for storing the addition-curable liquid organosilicon composition according to claim 1, wherein, The member having the function of consuming and removing oxygen and moisture is composed of a dehydrating and deoxidizing agent, or a combination of a dehydrating agent and a deoxidizing agent.

15. The container for storing the addition-curing type liquid organosilicon composition according to claim 1, wherein, A member having the function of consuming and removing oxygen and moisture is provided in the gap between the first sealing structure and the second sealing structure.

16. The container for storing the addition-curing type liquid organosilicon composition according to claim 1, wherein, The member having the function of consuming and removing oxygen and moisture is disposed on the sealing part of the first sealing structure.

17. The container for storing the addition-curable liquid organosilicon composition according to claim 1, wherein, The function of consuming and removing oxygen and moisture of the member having the function of consuming and removing oxygen and moisture is a function of chemically reacting with oxygen and moisture in the space where the member is present to absorb them.

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