JP2023147834A - Silane crosslinkable silicone rubber composition, silane crosslinked silicone rubber molded body and method for producing them, and silane crosslinked silicone rubber molded article - Google Patents

Abstract

To provide a silane crosslinkable silicone rubber composition which enables production of a silane crosslinked silicone rubber molded body that is excellent in appearance, and exhibits high heat resistance and strength with excellent producibility and a method for producing the same, and a silane crosslinked silicone rubber molded body exhibiting the excellent characteristics and a method for producing the same, and a silane crosslinked silicone rubber molded article.SOLUTION: There are provided a silane crosslinkable silicone rubber composition which contains, with respect to 100 pts.mass of a base rubber containing a millable type silicone rubber and fluororubber, 1-15 pts.mass of a silane coupling agent that is graft-bonded to the base rubber, 0.5-100 pts.mass of an inorganic filler, and 0.01-0.5 pts.mass of a silanol condensation catalyst and a method for producing the same; a silane crosslinked silicone rubber molded body using the silane crosslinkable silicone rubber composition and a method for producing the same; and a silane crosslinked silicone rubber molded article including the silane crosslinked silicone rubber molded body.SELECTED DRAWING: None

Description

The present invention relates to a silane crosslinked silicone rubber composition, a silane crosslinked silicone rubber molded article, a method for producing the same, and a silane crosslinked silicone rubber molded article using the silane crosslinked silicone rubber molded article.

As a coating layer (insulator, sheath, etc.) provided on wiring materials such as insulated wires, cables, cords, optical fiber cores, or optical fiber cords (optical fiber cables) used in the electrical/electronic equipment field and industrial field. Various resin molded bodies or rubber molded bodies are used as various molded bodies such as packing and sheets. Such molded bodies are required to have properties depending on their intended use, such as appearance properties, strength (e.g. tensile strength), and even heat resistance from the viewpoint of safety and reliability. .
Examples of materials for forming such molded bodies include silicone rubber that can exhibit excellent weather resistance, heat resistance, etc. through chemical crosslinking. Regarding molded products using silicone rubber, for example, Patent Document 1 describes "an insulated wire in which the periphery of a conductor is covered with an insulating layer containing crosslinked silicone rubber, the insulating layer containing an acid acceptor. "An insulated wire characterized by the fact that it is Further, Patent Document 2 states, “In an insulated wire in which the periphery of the conductor is coated with an insulating layer containing crosslinked silicone rubber, the insulating layer has a Shore A hardness of 50 or more as measured in accordance with JIS K6253. , an insulated wire characterized by containing an oxide of a transition metal.

JP2016-091911A Japanese Patent Application Publication No. 2015-090753

The insulated wires described in Patent Documents 1 and 2 both have an insulating layer containing crosslinked silicone rubber. Conventionally, as a crosslinking method for silicone rubber (the final crosslinking method after molding), a self-crosslinking method by heating or a chemical crosslinking method using a crosslinking agent has been adopted. Therefore, for crosslinking silicone rubber, it is essential to carry out a crosslinking reaction at a high temperature using, for example, crosslinking equipment such as a chemical crosslinking pipe. For example, in Patent Documents 1 and 2, the crosslinking reaction is carried out at 200° C. for 4 hours. As described above, the conventional crosslinking method for silicone rubber has manufacturability (manufacturing) problems in terms of preparation and maintenance of crosslinking equipment, as well as crosslinking conditions. In particular, in recent years, from the perspective of protecting and sustaining the global environment, there has been an increasing demand for improved productivity and reduced manufacturing costs. A technology that can do this is desired.

Incidentally, in recent years, the uses of various molded bodies have been diversified and the quality of molded bodies has been improved. With this progress, molded bodies are required to have higher levels of heat resistance and strength than ever before.

The present invention solves the above-mentioned problems and provides a silane-crosslinked silicone rubber composition capable of producing a silane-crosslinked silicone rubber molded article having excellent appearance, high heat resistance and strength with excellent manufacturability, and the production thereof. The task is to provide a method. Another object of the present invention is to provide a silane-crosslinked silicone rubber molded article that has an excellent appearance and exhibits high heat resistance and strength, and a method for producing the same. Furthermore, it is an object of the present invention to provide a silane-crosslinked silicone rubber molded article using a silane-crosslinked silicone rubber molded article exhibiting the above-mentioned excellent properties.

The present inventors added 1 to 15 parts by mass of a silane coupling agent grafted to the base rubber and 0.00 parts by mass of an inorganic filler to 100 parts by mass of a base rubber containing millable silicone rubber (organopolysiloxane). A silane crosslinkable silicone rubber composition containing 5 to 300 parts by mass and 0.01 to 0.5 parts by mass of a silanol condensation catalyst can be silane crosslinked under relatively mild conditions without using special crosslinking equipment. The inventors have discovered that it is possible to produce a silane crosslinked product with excellent appearance, heat resistance, and strength by causing a reaction, and as a result, solving the problem of manufacturability. Based on this knowledge, we conducted various studies on the physical properties and behavior of this silane crosslinkable silicone rubber composition, and found that it is necessary to further improve the heat resistance and strength of molded products in order to meet the recent demands for increasing the heat resistance and strength to a high level. It turns out that there is room for improvement. Therefore, as a result of further studies on the above-mentioned silane-crosslinkable silicone rubber composition, we found that although it is based on the silane-crosslinkable silicone rubber composition of the above composition, fluororubber is used in combination with millable silicone rubber as the base rubber. Then, by reducing the content of inorganic filler to 100 parts by mass or less, we can create a silane crosslinked silicone rubber molded product with high heat resistance and strength while maintaining excellent appearance and without impairing excellent manufacturability. We have found that this can be expressed. The present inventors have conducted further research based on these findings and have completed the present invention.

That is, the object of the present invention was achieved by the following means.
<1> 1 to 15 parts by mass of a silane coupling agent grafted to the base rubber and 0.5 to 100 parts by mass of an inorganic filler to 100 parts by mass of a base rubber containing millable silicone rubber and fluororubber. A silane crosslinkable silicone rubber composition containing 0.01 to 0.5 parts by mass of a silanol condensation catalyst.
<2> The silane crosslinkable silicone rubber composition according to <1>, wherein the fluororubber includes tetrafluoroethylene-propylene rubber.
<3> The silane crosslinkable silicone rubber composition according to <1> or <2>, wherein the base rubber contains an ethylene copolymer resin.
<4> The silane according to any one of <1> to <3>, wherein the inorganic filler is at least one selected from metal hydrates, talc, clay, silica, calcium carbonate, and carbon black. Crosslinkable silicone rubber composition.
<5> The silane crosslinkable silicone rubber composition according to any one of <1> to <4>, wherein the content of the silane coupling agent is 3 to 15 parts by mass based on 100 parts by mass of the base rubber. thing.
<6> A silane crosslinked silicone rubber molded article obtained by molding the silane crosslinkable silicone rubber composition according to any one of <1> to <5> above and then contacting it with water.
<7> A silane crosslinked silicone rubber molded article comprising the silane crosslinked silicone rubber molded article according to <6> above.

<8> For 100 parts by mass of a base rubber containing millable silicone rubber and fluororubber, 1 to 15 parts by mass of a silane coupling agent having a grafting reaction site capable of grafting to the base rubber, and 0 parts by mass of an inorganic filler. A silane crosslinkable silicone rubber composition is obtained by mixing .5 to 100 parts by mass, 0.01 to 0.6 parts by mass of an organic peroxide, and 0.01 to 0.5 parts by mass of a silanol condensation catalyst. A method for producing a silane crosslinkable silicone rubber composition, comprising step (1),
The step (1) includes the following step (a) and step (c), provided that when a part of the base rubber is melt-mixed in the following step (a), the following step (a) and step ( A method for producing a silane crosslinkable silicone rubber composition, comprising b) and step (c).
Step (a): All or part of the base rubber, the silane coupling agent, and the
The inorganic filler and the organic peroxide are heated at a temperature below the decomposition temperature of the organic peroxide.
Step (b): melt-mixing the remainder of the base rubber and the silanol condensation catalyst at a temperature above to prepare a silane masterbatch.
Step (c) of preparing a medium masterbatch: the silane masterbatch and the silanol condensation catalyst or the catalyst masterbatch.
The process of mixing with starbatch,
<9> A method for producing a silane-crosslinked silicone rubber molded article comprising the following steps (1), (2) and (3),
Step (1): 100 mass of base rubber containing millable silicone rubber and fluororubber
%, a grafting reaction part capable of grafting reaction to the base rubber
1 to 15 parts by mass of a silane coupling agent having 1 to 15 parts by mass, and 0.0 parts by mass of an inorganic filler.
5 to 100 parts by mass, 0.01 to 0.6 parts by mass of organic peroxide, and cyano
0.01 to 0.5 parts by mass of a silane-crosslinkable silica
Step (2): Molding the silane crosslinkable silicone rubber composition to obtain a molded article Step (3): Bringing the molded article into contact with water to obtain a silane crosslinked silicone rubber molded article engineering
Step (1) includes the following step (a) and step (c), provided that in the case where a part of the base rubber is melt-mixed in the following step (a), the following step (a) and step A method for producing a silane-crosslinked silicone rubber molded article, comprising (b) and step (c).
Step (a): All or part of the base rubber, the silane coupling agent, and the
The inorganic filler and the organic peroxide are heated at a temperature below the decomposition temperature of the organic peroxide.
Step (b): melt-mixing the remainder of the base rubber and the silanol condensation catalyst at a temperature above to prepare a silane masterbatch.
Step (c) of preparing a medium masterbatch: the silane masterbatch and the silanol condensation catalyst or the catalyst masterbatch.
Process of mixing with starbatch

In the present invention, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits. In addition, in the present invention, when multiple numerical ranges are set and explained regarding the content of components, physical properties, etc., the upper and lower limits forming the numerical range are written before and after "~" as a specific numerical range. The numerical value ranges are not limited to the specific combinations described above, and can be set as numerical ranges in which the upper and lower limit values of each numerical range are appropriately combined.
Furthermore, in the present invention, "(meth)acrylic acid" refers to either or both of acrylic acid and methacrylic acid, and "(meth)acrylic ester" refers to either acrylic ester or methacrylic ester. or both.

The present invention can provide a silane-crosslinked silicone rubber composition capable of producing a silane-crosslinked silicone rubber molded article having excellent appearance, high heat resistance, and strength with excellent manufacturability, and a method for producing the same. Further, the present invention can provide a silane-crosslinked silicone rubber molded article with excellent appearance and high heat resistance and strength, and a method for producing the silane-crosslinked silicone rubber molded article. Furthermore, the present invention can provide a silane-crosslinked silicone rubber molded article using the silane-crosslinked silicone rubber molded article exhibiting the above-mentioned excellent properties.

[Silane crosslinkable silicone rubber composition]
The silane crosslinkable silicone rubber composition of the present invention contains 1 to 15 parts by mass of a silane coupling agent grafted to the base rubber, based on 100 parts by mass of a base rubber containing millable silicone rubber and fluororubber. , 0.5 to 100 parts by mass of an inorganic filler, and 0.01 to 0.5 parts by mass of a silanol condensation catalyst. This silane crosslinkable silicone rubber composition can be prepared by appropriately mixing the above components, but is preferably prepared by the method for producing a silane crosslinkable silicone rubber composition of the present invention, which will be described later. The silane crosslinkable silicone rubber composition can also be referred to as a molten mixture of a silane masterbatch and a silanol condensation catalyst or catalyst masterbatch, which will be described later.

Although details will be described later, the silane crosslinkable silicone rubber composition of the present invention has a silane coupling agent bonded to or dissociated from an inorganic filler that is grafted to a millable silicone rubber (organopolysiloxane) (grafting reaction). Contains silane crosslinkable silicone rubber.

This silane crosslinkable silicone rubber composition generates a silanol condensation reaction under mild conditions without requiring special crosslinking equipment such as a chemical crosslinking tube or an electron beam crosslinker, resulting in excellent manufacturability and an excellent appearance. , it is possible to produce a silane-crosslinked silicone rubber molded product that exhibits high heat resistance and strength. Therefore, the silane crosslinkable silicone rubber composition of the present invention is suitably used in the method for producing a silane crosslinked silicone rubber molded article of the present invention or the silane crosslinked silicone rubber molded article of the present invention.

In general, silicone rubber, especially millable silicone rubber that exhibits a pale (clay-like) shape in a bulk state, is difficult to mix and mold, and the moldability requires specialized silicone rubber manufacturing equipment (mixer, extruder, etc.). I have this problem. However, as will be described later, when an ethylene copolymer resin is used in combination with millable silicone rubber and fluororubber as a base resin, it can be used for general-purpose plastic molding without impairing the excellent manufacturability and excellent properties of the molded product. Even with a machine (hereinafter also referred to as a general-purpose extrusion molding machine), extrusion molding can be performed, and the problem of moldability can be solved. Such a silane-crosslinkable silicone rubber composition of the present invention can overcome the limitations of handling and manufacturing equipment in the production of silicone rubber moldings, and has great advantages. In addition, when this silane crosslinkable silicone rubber composition is applied to both of the above production methods of the present invention (aspects for producing a catalyst masterbatch), a silane masterbatch and a catalyst master which are intermediate products of the silane crosslinkable silicone rubber composition are produced. Batches can be prepared together as non-stick pellets.

[Silane crosslinked silicone rubber molded product]
The silane crosslinked silicone rubber molded article of the present invention is a crosslinked silicone rubber molded article obtained by subjecting the silane crosslinkable silicone rubber composition of the present invention to silane crosslinking (silanol condensation reaction) after molding. A molded body made of a condensate). The silane-crosslinked silicone rubber molded product of the present invention has a crosslinked structure at the crosslinking point (vinyl group) of millable silicone rubber (organopolysiloxane) and also has a crosslinked structure involving an inorganic filler, but is similar to fluororubber. They are compatible and exhibit a high level of heat resistance and strength without impairing their excellent appearance.

Although details will be described later, the silane-crosslinked silicone rubber molded article of the present invention has a crosslinked structure in which millable silicone rubber is crosslinked with silane (a crosslinked structure via a silane coupling agent or a silanol condensate thereof). It is thought that an inorganic filler is incorporated into a part of this crosslinked structure, as will be described later.
The silane crosslinked silicone rubber molded article of the present invention is molded into an appropriate shape and size depending on the use, for example, the use of the silane crosslinked silicone rubber molded article of the present invention described below.

Each component used in the present invention will be explained below.
Each component can be used alone or in combination of two or more.
In the present invention, the term "rubber" is used to include elastomers, unless otherwise specified.
<Base rubber>
The base rubber used in the present invention contains millable silicone rubber and fluororubber as essential components, and may also contain other rubbers or various resins as optional components.

(Millable silicone rubber)
Millable silicone rubber is used as a compound made of linear organopolysiloxane (uncrosslinked) as the main raw material (silicone raw rubber) and a reinforcing agent, usually silica.
Millable silicone rubber exhibits high thermal stability even above the decomposition temperature of organic peroxides (180° C.), has good workability, and can cause a grafting reaction with a silane coupling agent. According to the studies of the present inventors, even in the presence of a specific amount of inorganic filler, organopolysiloxanes that are not pre-blended with reinforcing agents are clay-like solids, gum-like substances, or liquid substances. It has been revealed that even if it has a crosslinking point (vinyl group), it is not easily susceptible to the grafting reaction of a silane coupling agent, and the silane crosslinking method cannot be applied to it. Furthermore, organopolysiloxanes (millable silicone rubbers) that have been blended with reinforcing agents in advance are more susceptible to grafting reactions with silane coupling agents than crosslinking reactions between organopolysiloxanes, even in the presence of a specific amount of inorganic filler. It has been found that silane coupling agents can occur preferentially to produce grafted organopolysiloxanes. Based on this knowledge, the present invention involves grafting a silane coupling agent to a millable silicone rubber as a compound in a state in which fluororubber and a specific amount of inorganic filler are separately co-existed to form a silane crosslinking agent. It makes the law applicable.

The above-mentioned organopolysiloxane may be any organopolysiloxane as long as it can undergo a grafting reaction with the silane coupling agent, and examples thereof include organopolysiloxanes containing vinyl groups as sites (crosslinking points) capable of grafting reaction. , methylvinylpolysiloxane, methylphenylvinylpolysiloxane, methylfluoroalkylpolysiloxane, and the like. Fluoroalkyl is not particularly limited, and includes, for example, 3,3,3-trifluoropropyl group. Note that the terminal group of the organopolysiloxane is not particularly limited, and examples thereof include an alkyl group (methyl group), a vinyl group, and a hydroxyl group.
The content of vinyl groups in the organopolysiloxane is not particularly limited, and can be appropriately determined depending on the degree of crosslinking, and can be, for example, 0.025 to 1.0 (mol%). The content of vinyl groups can be measured, for example, by infrared absorption spectroscopy (FT-IR) or proton NMR ( ¹ H-NMR). The respective contents of phenyl groups and fluoroalkyl groups in the organopolysiloxane are not particularly limited, and are appropriately determined depending on the use, required characteristics, and the like. Further, the degree of polymerization of the organopolysiloxane is not particularly limited, and can be, for example, 3,000 to 10,000.

Millable silicone rubber contains a reinforcing agent (filler). The reinforcing agent is not particularly limited, and examples thereof include various silicas such as fumed silica (also referred to as fumed silica and dry silica), precipitated silica, diatomaceous earth, and quartz powder, and surface-treated silicas thereof. As the reinforcing agent, fumed silica is preferable from the viewpoints of moldability, appearance of the molded product, insulation resistance, etc. The BET specific surface area of the reinforcing agent is not particularly limited, but is preferably about 50 to 300 m ² /g, for example. The method for measuring the BET specific surface area is, for example, in accordance with the method specified in Japanese Industrial Standards (JIS) Z 8830 (2013), in which gas molecules such as nitrogen gas whose adsorption occupied area is known are applied to the surface of powder particles. The specific surface area of the sample can be determined from the amount of adsorption (BET method).

The specific gravity of the millable silicone rubber (before the silane coupling agent is grafted) is not particularly limited, and can be appropriately set depending on the use, required characteristics, etc. When the specific gravity of the millable silicone rubber is low, the reinforcing agent content in the millable silicone rubber is reduced, so the compatibility (fluidity) of the base rubber during molding of the silane crosslinked silicone rubber composition is improved. As a result, by using millable silicone rubber with a low specific gravity, it can be molded with a general-purpose extrusion molding machine without sacrificing excellent manufacturability, and it is also possible to achieve high heat resistance and strength while maintaining an excellent appearance. The specific gravity of the millable silicone rubber can be set to 1.05 to 1.50 g/cm ³ in order to solve the problem of moldability while achieving a high level of heat resistance and strength in a well-balanced manner. It is preferably 1.05 to 1.25 g/cm ³ , more preferably 1.10 to 1.20 g/cm ³ , even more preferably 1.10 to 1.15 g/cm ³ , Particularly preferred is 1.11 to 1.14 g/cm ³ . The specific gravity of the millable silicone rubber is a value measured by the method described in Examples below.

The content of the reinforcing agent in the millable silicone rubber is not particularly limited as long as the specific gravity of the millable silicone rubber falls within the above range, and can be set as appropriate depending on the specific gravity, use, required characteristics, etc. can. For example, the content of the reinforcing agent in the millable silicone rubber may vary depending on the specific gravity of the reinforcing agent, etc., but may range from 10 to 40% by mass, and from 12 to 40% by mass based on 100% by mass of the millable silicone rubber. It is preferably 38% by mass, more preferably 14 to 35% by mass.
The millable silicone rubber may contain fillers other than reinforcing agents, dispersion promoters, and other additives, for example, within a range that satisfies the above specific gravity.

The millable silicone rubber may be prepared by mixing an organopolysiloxane, a reinforcing agent, and the above additives as appropriate, or a commercially available product (a compound containing no crosslinking agent (curing agent)) may be used. Commercially available products include, for example, ELASTSIL R401 series (manufactured by Asahi Kasei Wacker), XIAMETER RBB6660 series (manufactured by Dow Corning), rubber compound KE series (manufactured by Shin-Etsu Silicone), millable silicone rubber TSE series (manufactured by Momentive), etc. can be mentioned.

(Fluororubber)
The base rubber used in the present invention contains fluororubber as an essential component. When fluororubber is contained, the silane-crosslinked silicone rubber molded article can exhibit a high level of heat resistance and strength, and can be made into a molded article that does not melt even at high temperatures. Here, heat resistance that does not melt even at high temperatures refers to a property that does not melt at a temperature of preferably 200°C, more preferably at a temperature of 200°C or higher. There is no upper limit to the temperature at which the silane-crosslinked silicone rubber molded product does not melt, but 300°C or less is practical.
The fluororubber is not particularly limited, and conventional fluororubbers conventionally used in various rubber moldings can be used. Examples of the fluororubber include homopolymer or copolymer rubber containing fluorine atoms in the main chain or side chain. Fluororubber is usually obtained by (co)polymerizing monomers containing fluorine atoms.

Such fluororubbers include, but are not particularly limited to, fluorocarbon monomers such as perfluorohydrocarbons such as tetrafluoroethylene and hexafluoropropylene, and partially fluorinated hydrocarbons such as vinylidene fluoride. Examples include polymer rubbers and copolymer rubbers of these fluorine-containing monomers and hydrocarbons such as ethylene and/or propylene. Specifically, tetrafluoroethylene-propylene copolymer rubber (FEPM), tetrafluoroethylene-fluorinated (e.g. hexafluoro)propylene copolymer rubber, tetrafluoroethylene-perfluorovinylether copolymer rubber (FFKM), Examples include vinylidene fluoride rubber (FKM, for example, vinylidene fluoride-hexafluoropropylene copolymer rubber). Further examples include copolymer rubbers of the above-mentioned fluorine-containing monomers and chloroprene and/or chlorosulfonated polyethylene. Among these fluororubbers, tetrafluoroethylene-propylene copolymer rubber and vinylidene fluoride-hexafluoropropylene copolymer rubber are preferred, and tetrafluoroethylene-propylene copolymer rubber is more preferred.

The fluorine atom content in the fluororubber (the mass ratio of fluorine atoms to the total amount of fluororubber) is not particularly limited, but is preferably 25% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit of the fluorine content is the mass percentage when all the hydrogen atoms that can be replaced with fluorine atoms in the polymer before fluorination are replaced with fluorine atoms, and the molecular weight of the polymer before fluorination, the fluorine It cannot be determined uniquely depending on the number of hydrogen atoms that can be replaced by atoms. For example, it can be 75% by mass. In the present invention, the fluorine content is determined by a calculated value during synthesis or by a potassium carbonate thermal decomposition method. Examples of the potassium carbonate thermal decomposition method include the method described by Makoto Noshiro et al., Nikka, 6, 1236 (1973).

The fluororubber may be synthesized as appropriate, or a commercially available product may be used.
For example, examples of tetrafluoroethylene-propylene copolymer rubber (FEPM) include Aflas (trade name, manufactured by Asahi Glass Co., Ltd.). Examples of the tetrafluoroethylene-perfluorovinylether copolymer rubber (FFKM) include Kalrez (trade name, manufactured by DuPont). Examples of vinylidene fluoride rubber (FKM) include Viton (trade name, manufactured by DuPont), Daiel (trade name, manufactured by Daikin Industries, Ltd.), Dyneon (trade name, manufactured by 3M), and Tecnoflon (trade name, manufactured by Solvay). ) etc.

The base rubber can contain rubbers, resins, etc. other than millable silicone rubber and other than fluororubber. Examples of the resin include polyolefin resins, and examples of the rubber include rubbers and elastomers such as polymers forming polyolefin resins.

(Polyolefin resin)
The polyolefin resin that the base rubber may contain is not particularly limited, and includes resins made of polymers obtained by homopolymerizing or copolymerizing olefin compounds, such as known resins used in various resin compositions. I can list the following. Specifically, resins such as polyethylene (PE), polypropylene (PP), and polyolefin copolymers having an acid copolymerization component or an acid ester copolymerization component can be mentioned. The polyolefin resin is preferably a polyethylene resin, a polypropylene resin, or a polyolefin copolymer resin having an acid copolymerization component or an acid ester copolymerization component (sometimes referred to as ethylene copolymer resin). Note that the polyolefin resin may be acid-modified with a commonly used unsaturated carboxylic acid or a derivative thereof.

- Polyethylene resin -
The polyethylene resin (PE) is not particularly limited as long as it is a polymer resin whose main component is ethylene. Examples include high-density polyethylene (HDPE), low-density polyethylene (LDPE), ultra-high molecular weight polyethylene (UHMW-PE), linear low-density polyethylene (LLDPE), and very low-density polyethylene (VLDPE).

- Polypropylene resin -
The polypropylene resin (PP) is not particularly limited as long as it is a polymer resin whose main component is propylene. Examples include propylene homopolymers as well as random polypropylene and block polypropylene resins.
It is preferable to use polyethylene resin, polypropylene resin, etc. together with the following ethylene copolymer resin as a polyolefin resin. That is, when the base rubber contains a polyethylene resin or a polypropylene resin, it is preferable that the base rubber contains an ethylene copolymer resin in terms of heat resistance and the like.

- Ethylene copolymer resin -
In the present invention, the ethylene copolymer resin refers to an ethylene copolymer resin having an acid copolymer component or an acid ester copolymer component among copolymer resins containing ethylene as a copolymer component. That is, even if the copolymer resin contains ethylene as a copolymerization component, a resin that does not have an acid copolymerization component or an acid ester copolymerization component is not included in the ethylene copolymer resin.
In the present invention, when the base rubber contains an ethylene copolymer resin, while maintaining or improving the remarkable heat resistance and strength of the silane-crosslinked silicone rubber molded article, it is possible to manufacture it using general-purpose manufacturing equipment, especially general-purpose manufacturing equipment. Extrusion molding becomes possible with an extrusion molding machine. In addition, in the method for producing a silane crosslinkable silicone rubber composition of the present invention (a mode of producing a catalyst masterbatch) described below, the silane masterbatch and catalyst masterbatch, which are intermediate products thereof, can be pelletized. Moreover, pellet fusion (blocking) can also be suppressed. Although the details of the reason for the above-mentioned effects are not yet clear, by coexisting an ethylene copolymer resin in the silane crosslinking method, the silane coupling agent is preferentially applied to the millable silicone rubber during the grafting reaction. This is thought to be because the fluidity of the reaction system can be increased without inhibiting the selective grafting reaction, and as a result, the molten mixture during extrusion also maintains high fluidity.

Compounds that lead to acid copolymerization components or acid ester copolymerization components in the ethylene copolymer resin are not particularly limited, and include carboxylic acid compounds such as (meth)acrylic acid, vinyl acetate, alkyl (meth)acrylates, etc. Examples include acid ester compounds. The alkyl group of the alkyl (meth)acrylate preferably has 1 to 12 carbon atoms.
Examples of such ethylene copolymer resins include ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid ester copolymer, and ethylene-(meth)acrylic acid copolymer resin. can be mentioned. The resin made of ethylene-(meth)acrylic acid ester copolymer and ethylene-(meth)acrylic acid copolymer is not particularly limited, and ordinary resins can be used. The (meth)acrylic ester that forms the ethylene-(meth)acrylic ester copolymer is not particularly limited, but includes esters of (meth)acrylic acid and alcohols having 1 to 12 carbon atoms. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. Can be mentioned. Examples of the ethylene-(meth)acrylate copolymer resin include ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate copolymer. (EBA).
Among these, ethylene-vinyl acetate copolymer (EVA) and ethylene-(meth)acrylic acid ester copolymer are preferred from the viewpoint of compatibility with silicone rubber, strength characteristics, heat resistance, etc. Ethyl acrylate copolymer (EEA) resin is more preferred.
The content of the copolymer component in the ethylene copolymer resin is not particularly limited and can be set as appropriate, but the content of the copolymer component is preferably 15 to 45% by mass.

(Rubber other than millable silicone rubber)
Rubbers other than millable silicone rubber and other than fluororubber are not particularly limited, and include known rubbers used in various rubber compositions. Specific examples include ethylene-α-olefin copolymer rubber, styrene elastomer, and acrylic rubber.

- Ethylene-α-olefin copolymer rubber -
The ethylene-α-olefin copolymer rubber (also referred to as ethylene rubber in the present invention) is not particularly limited as long as it is a copolymer rubber obtained by copolymerizing ethylene and α-olefin, and known rubbers can be used. can do. Preferable examples of the ethylene-α-olefin copolymer rubber include a binary copolymer rubber of ethylene and an α-olefin, a terpolymer rubber of ethylene, an α-olefin, and a diene compound, and the like. The α-olefin is not particularly limited, and α-olefins having 3 to 12 carbon atoms are preferred. Further, the diene compound constituting the terpolymer is not particularly limited, and examples include conjugated diene compounds such as butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, dicyclo Examples include non-conjugated diene compounds such as pentadiene (DCPD), ethylidenenorbornene (ENB), and 1,4-hexadiene, with non-conjugated diene compounds being preferred. As the binary copolymer rubber, ethylene-propylene rubber (EPM) is preferred, and as the terpolymer rubber, ethylene-propylene-diene rubber (EPDM) is preferred.

- Styrenic elastomer -
A styrenic elastomer is an elastomer made of a polymer having a component derived from an aromatic vinyl compound in the molecule. Examples of such styrenic elastomers include block copolymers and random copolymers of a conjugated diene compound and an aromatic vinyl compound, and hydrogenated products thereof. More specifically, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), hydrogenated SIS, styrene-butadiene-styrene block copolymer (SBS) , hydrogenated SBS, styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene Examples include rubber (HSBR).

- Acrylic rubber -
Acrylic rubber (also referred to as ethylene-acrylic rubber) includes rubber obtained by copolymerizing at least ethylene and an acrylic acid alkyl ester as constituent components. The acrylic acid alkyl ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, and the like.
As the acrylic rubber, various copolymer rubbers such as a binary copolymer of ethylene and an acrylic acid alkyl ester, and a terpolymer obtained by copolymerizing this with a copolymer component containing a carboxyl group are preferably used. can be used. The copolymerization component containing a carboxyl group is not particularly limited, and examples thereof include (meth)acrylic acid, maleic acid, and the like.

(mineral oil)
The base rubber can also contain mineral oil. Examples of the mineral oil include paraffin oil, naphthenic oil, and aromatic oil, with paraffin oil being preferred. Mineral oil is particularly preferably contained together with the elastomer.

(Composition of base rubber)
The base rubber contains each component at the following content so that the total amount is 100% by mass. In addition, when the base rubber contains a plurality of each component, the content of the component is the total content of the plurality of components.
The content of the millable silicone rubber in 100% by mass of the base rubber is not particularly limited, but is preferably 30 to 80% by mass since it can build a sufficient crosslinked structure while solving moldability problems. The content is more preferably 35 to 70% by mass, even more preferably 40 to 60% by mass, and even more preferably 40 to 55% by mass, in terms of achieving higher levels of appearance, heat resistance, and strength. Particularly preferred.
The content of fluororubber in 100% by mass of the base rubber is not particularly limited, but it is preferably 5 to 40% by mass in order to achieve high heat resistance and strength while solving moldability problems. Preferably, it is more preferably 10 to 35% by mass, even more preferably 12 to 32% by mass, and even more preferably 15 to 30% by mass, in that it can achieve both heat resistance and tensile strength at a higher level in a well-balanced manner. It is particularly preferable that there be.

The total content of the polyolefin resin in 100% by mass of the base rubber is not particularly limited and is appropriately determined. For example, it is preferably 0 to 70% by weight, more preferably 5 to 50% by weight, and even more preferably 10 to 40% by weight.
The content of polyethylene resin in 100% by mass of the base rubber is not particularly limited, and is appropriately set in consideration of the total content of the polyolefin resin, for example, preferably 0 to 25% by mass, and 5% by mass. More preferably, it is 20% by mass. Similarly, the content of polypropylene resin in 100% by mass of the base rubber is not particularly limited, and is appropriately set in consideration of the total content of the polyolefin resin, and may be, for example, 0 to 25% by mass. It is preferably 2 to 20% by mass, and more preferably 2 to 20% by mass. The content of the ethylene copolymer resin in 100% by mass of the base rubber is not particularly limited, and is appropriately set in consideration of the total content of the polyolefin resin. For example, it is preferably 5 to 30% by mass, and 10 to 30% by mass, in order to solve moldability problems while achieving good appearance, heat resistance, and tensile strength of the silane crosslinked silicone rubber molded product. More preferably, it is 15 to 25% by mass.

The total content of rubbers other than millable silicone rubber and other than fluororubber in 100% by mass of the base rubber is not particularly limited and is appropriately determined. For example, it is preferably 0 to 50% by weight, more preferably 5 to 45% by weight, and even more preferably 8 to 40% by weight.
The content of the ethylene-α olefin copolymer rubber in 100% by mass of the base rubber is not particularly limited, and is appropriately set in consideration of the total content of the above rubber, for example, 0 to 25% by mass. The content is preferably 0 to 20% by mass, more preferably 0 to 15% by mass. The content of the styrene elastomer in 100% by mass of the base rubber is not particularly limited, and is appropriately set in consideration of the total content of the rubber, for example, preferably 0 to 25% by mass, and 0 to 25% by mass. More preferably, it is 15% by mass. The content of acrylic rubber in 100% by mass of the base rubber is not particularly limited, and is appropriately set in consideration of the total content of the rubber, and can be, for example, 8 to 40% by mass.

The content of mineral oil in 100% by mass of the base rubber is not particularly limited and is appropriately determined. For example, it is preferably 0 to 25% by weight, more preferably 0 to 20% by weight.

<Silane coupling agent>
The silane crosslinkable silicone rubber composition contains a silane coupling agent grafted onto a base rubber, particularly a millable silicone rubber. The base rubber to which the silane coupling agent is grafted is preferably prepared by a grafting reaction between the silane coupling agent and the base rubber in step (a) described below.
The silane coupling agent used in the present invention (before the grafting reaction) undergoes a grafting reaction in the presence of radicals generated by decomposition of an organic peroxide to a site where the grafting reaction is possible in the base rubber. It has a moiety (an atom or a functional group such as an ethylenically unsaturated group). Moreover, it is preferable that it has a hydrolyzable silyl group as a reactive site capable of silanol condensation, and can react with a chemically bondable site of the inorganic filler. The silane coupling agent that can be used in the present invention is not particularly limited, and includes silane coupling agents used in conventional silane crosslinking methods.
As the silane coupling agent, silane coupling agents having an ethylenically unsaturated group and a hydrolyzable silyl group are preferably mentioned, and specifically, vinyltrimethoxylan, vinyltriethoxylan, vinyltributoxylan, Vinyl alkoxyranes such as vinyl dimethoxyethoxylan, vinyl dimethoxy butoxyran, vinyl diethoxy butoxylan, allyltrimethoxylan, allyltriethoxylan, vinyltriacetoxylan, methacryloxypropyltrimethoxyrane, methacryloxypropyltriethoxyrane, Examples include (meth)acryloxyalkoxylans such as methacryloxypropylmethyldimethoxylane. Among them, vinyltrimethoxylan or vinyltriethoxylan is particularly preferred.

<Inorganic filler>
The inorganic filler is not particularly limited, but it is preferable to have a site on its surface that can be chemically bonded to a reactive site capable of silanol condensation of the silane coupling agent through a hydrogen bond, a covalent bond, or an intermolecular bond. Sites that can chemically bond with the reaction site of the silane coupling agent are not particularly limited, but include OH groups (hydroxyl groups, water molecules containing water or crystal water, OH groups such as carboxy groups), amino groups, SH groups, etc. It will be done.
Specific examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, boehmite, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and aluminum borate. , whiskers, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, talc, and other metal hydrates such as compounds having hydroxyl groups or water of crystallization. In addition, boron nitride, silica (crystalline silica, amorphous silica, etc.), carbon black, clay (fired clay), zinc oxide, tin oxide, titanium oxide, molybdenum oxide, silicone compounds, quartz, zinc borate, white carbon , zinc borate, zinc hydroxystannate, zinc stannate, and the like. The inorganic filler preferably contains at least one of metal hydrates, talc, clay, silica, calcium carbonate, and carbon black, and silica is more preferred in terms of heat resistance and tensile strength.
As the inorganic filler, a surface-treated inorganic filler whose surface is treated with a silane coupling agent or the like can be used. The amount of surface treatment is not particularly limited, but is preferably 3% by mass or less, for example.

<Silanol condensation catalyst>
The silanol condensation catalyst has the function of causing (promoting) a condensation reaction in the presence of water at a reaction site capable of silanol condensation of the silane coupling agent grafted onto the base rubber. Based on the action of this silanol condensation catalyst, the base rubber is crosslinked via the silane coupling agent.
Such a silanol condensation catalyst is not particularly limited, and examples thereof include organic tin compounds, metal soaps, platinum compounds, and the like. Examples of the organic tin compound include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate.

<Additives>
In the present invention, various additives commonly used in silicone rubber compositions can also be used. Such additives include, for example, antioxidants, lubricants, metal deactivators, plasticizers, flame retardants, flame retardant aids, plasticization reversion inhibitors, and even those other than those described for the base rubber. Examples include polymers.
Examples of the antioxidant include hindered phenol-based antioxidants, benzimidazole-based antioxidants, hydrazine-based heavy metal deactivators, and the like. Examples of the flame retardant (auxiliary) agent include brominated flame retardants, chlorine flame retardants, antimony trioxide, and the like.
In the present invention, the silane-crosslinked silicone rubber composition and the silane-crosslinked silicone rubber molded article contain any one or a combination of three of the above antioxidants, particularly a benzimidazole antioxidant, and the above-mentioned antioxidants. It includes any one or a combination of three antioxidants, particularly an embodiment that does not contain a benzimidazole antioxidant. In addition, in the embodiment containing an antioxidant, the total content of the antioxidant is preferably less than 30 parts by mass, and preferably 0.2 to 19 parts by mass, based on 100 parts by mass of the base rubber. The amount is more preferably 0.5 to 13 parts by mass. Containing no antioxidant is not limited to embodiments in which the content of each antioxidant in the silane crosslinkable silicone rubber composition is 0% by mass, but also includes embodiments in which it is contained within a range that does not impair the effects of the present invention. . As a range that does not impair the effects of the present invention, for example, the amount can be less than 0.2 parts by mass for hindered phenol antioxidants and hydrazine metal deactivators, and 1 part for benzimidazole antioxidants. It can be less than .5 parts by mass.
In the present invention, the crosslinkable silicone rubber composition and the silane crosslinked silicone rubber molded article include both embodiments containing a silicone rubber that does not contain a plasticization reversion inhibitor, such as a vinyl group-free silicone rubber, and embodiments that do not contain a plasticization reversion inhibitor. . When a plasticization reversion inhibitor is contained, its content can be 0.5 to 10% by mass in the base rubber. On the other hand, "not containing a plasticization reversion inhibitor" is not limited to an embodiment in which the content of the plasticization reversion prevention agent in the silane-crosslinkable silicone rubber composition is 0% by mass; For example, it includes an embodiment in which the content is less than 0.5 parts by mass, preferably 0.2 parts by mass or less, based on 100 parts by mass of the base rubber.

<Organic peroxide>
In the present invention, an organic peroxide is used when preparing a silane crosslinkable silicone rubber composition.
The organic peroxide generates radicals through thermal decomposition, thereby causing the grafting reaction of the silane coupling agent to the base rubber (the interaction between the grafting reaction site of the silane coupling agent and the grafting-reactable site of the base rubber). It has the function of promoting covalent bond-forming reactions (also called (radical) addition reactions). There are no particular restrictions on the organic peroxide, and for example, those with the general formula: R ¹ -OO-R ² , R ³ -OO-C(=O)R ⁴ , R ⁵ C(=O)-OO(C= O) A compound represented by R ⁶ is preferably used. Here, R ¹ to R ⁶ each independently represent an alkyl group, an aryl group, or an acyl group. Among R ¹ to R ⁶ of each compound, it is preferable that all of them are alkyl groups, or that one of them is an alkyl group and the rest are acyl groups.
The decomposition temperature of the organic peroxide is preferably 80 to 195°C, particularly preferably 125 to 180°C, as the decomposition temperature measured by the method described in JP 2016-121203A.
Examples of such organic peroxides include the organic peroxides described in paragraph [0036] of JP-A No. 2016-121203, and this description is hereby referred to and its contents are incorporated herein by reference. Incorporate it as part of the description. Among them, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane (Perhexa 25B), 2,5-dimethyl-2,5-di-(tert-butylperoxy) ) Hexin-3 is preferred.

(Composition of silane crosslinkable silicone rubber composition)
The content of the silane coupling agent grafted to the base rubber in the silane crosslinkable silicone rubber composition (content converted to the mass before grafting to the base rubber) is due to crosslinked gel, etc. It suppresses the formation of gel-shaped aggregates (gels) and the volatilization of the silane coupling agent, resulting in excellent appearance, formation of a sufficient crosslinked structure, and excellent heat resistance and mechanical properties (tensile strength, elongation at break). 1 to 15 parts by mass based on 100 parts by mass of the base rubber, in that it is possible to produce a silane-crosslinked silicone rubber molded product that exhibits the following. The content of the silane coupling agent is preferably 2 to 15 parts by mass, since it is possible to produce a silane-crosslinked silicone rubber molded product that has a good balance of appearance, tensile strength, and heat resistance. It is preferably 3 to 15 parts by mass. The upper limit is also preferably 8 parts by mass, since volatilization or self-condensation of the silane coupling agent can be suppressed and an excellent appearance can be achieved.
The content of the inorganic filler in the silane crosslinkable silicone rubber composition is particularly high in that it is possible to build a crosslinked structure in which the inorganic filler is involved in the silane crosslinked silicone rubber molding, thereby achieving both heat resistance and tensile strength. In terms of achieving heat resistance and strength, the amount is 0.5 to 100 parts by mass based on 100 parts by mass of the base rubber. The content of the inorganic filler is preferably set to a small amount in order to achieve both high heat resistance and tensile strength in a well-balanced manner, and specifically, it is preferably 3 to 50 parts by mass, and 3 to 50 parts by mass. It is more preferably 40 parts by weight, and particularly preferably 3 to 25 parts by weight.
The content of the silanol condensation catalyst in the silane crosslinkable silicone rubber composition is 0.01 to 0.5 parts by mass based on 100 parts by mass of the base rubber, in order to achieve a good balance between appearance, heat resistance, and tensile strength. It is preferably 0.03 to 0.3 parts by mass, more preferably 0.05 to 0.15 parts by mass.

The total content of additives (excluding antioxidants and plasticization reversion inhibitors) in the silane crosslinkable silicone rubber composition is not particularly limited, and may be determined as appropriate within the range that does not impair the effects of the present invention. Can be set.

(Composition of silane crosslinked silicone rubber molded body)
A silane crosslinked silicone rubber molded body is formed by molding a silane crosslinkable silicone rubber composition and then bringing it into contact with water to cause a silanol condensation reaction, so the content of each of the above components in this molded body is usually , the content is the same as in the silane crosslinkable silicone rubber composition. However, in the silane crosslinked silicone rubber molded article, the content of the silane coupling agent is the content before silanol condensation reaction, and the content of the base rubber is the content before crosslinking.

[Method for producing silane-crosslinked silicone rubber composition and silane-crosslinked silicone rubber molded article]
Hereinafter, a method for producing a silane crosslinkable silicone rubber composition of the present invention and a method for producing a silane crosslinkable silicone rubber molded article of the present invention will be explained.
The silane crosslinkable silicone rubber composition of the present invention is produced by carrying out the following step (1), and the silane crosslinked silicone rubber molded article of the present invention is produced by carrying out the following steps (1) to (3).
The method for producing a silane-crosslinked silicone rubber molded article and the method for producing a silane-crosslinkable silicone rubber composition of the present invention may be collectively referred to as the production method of the present invention.

Step (1): 100 parts by mass of base rubber containing millable silicone rubber and fluororubber
On the other hand, 1 to 15 parts by mass of silane coupling agent and 0.5 to 1 part of inorganic filler.
00 parts by mass, 0.01 to 0.6 parts by mass of organic peroxide, and silanol condensation catalyst.
A silane crosslinkable silicone rubber composition is prepared by mixing 0.01 to 0.5 parts by mass of a solvent.
Step of obtaining a product This step (1) includes the following steps (a) and (c). However, when a part of the base rubber is melt-mixed in the following step (a), the following steps (a), (b), and (c) are included.
Step (a): All or part of the base rubber, silane coupling agent, and inorganic filler
and an organic peroxide are melt-mixed at a temperature higher than the decomposition temperature of the organic peroxide.
Step (b): Melt and mix the remainder of the base rubber and the silanol condensation catalyst to prepare a catalyst masterbatch.
- Step of preparing a batch Step (c): Silane masterbatch and silanol condensation catalyst or catalyst masterbatch
The process of mixing

Step (2): Molding the silane crosslinkable silicone rubber composition to obtain a molded article Step (3): Contacting the molded article with water to obtain a silane crosslinked silicone rubber molded article

In the manufacturing method of the present invention, the mixing amount of each component used as the base rubber is the same as the above-mentioned content ratio explained as the composition of the base rubber. Further, the mixing amounts of the silane coupling agent, inorganic filler, silanol condensation catalyst, and additives are the same as the contents in the above-mentioned silane crosslinkable silicone rubber composition.
In the production method of the present invention, when a part of the base rubber is mixed in step (a), the polymer components to be mixed may be a specific component or two or more types of components. The proportion of the base rubber mixed in step (a) is preferably 60 to 95% by mass of the 100% by mass of the base rubber mixed in steps (a) and (b), and a sufficient crosslinked structure is constructed. The content is more preferably 70 to 95% by mass, since it is possible to achieve both heat resistance and mechanical properties at a higher level. The remainder of the base rubber (carrier resin) to be mixed in step (b) is appropriately determined depending on the part of the base rubber to be mixed in step (a).

However, in the manufacturing method of the present invention, the base rubber used in step (a) contains at least millable silicone rubber and fluororubber among the above components. As a result, the above-mentioned manufacturability problem can be solved and a sufficient silane crosslinked structure can be constructed in the silane crosslinked silicone rubber molded article, and a higher level of heat resistance and strength can be achieved in a well-balanced manner. Note that a part of the millable silicone rubber and fluororubber can also be used in step (b). The base rubber used in step (a) contains millable silicone rubber, fluororubber, and ethylene copolymer resin, which solves the above-mentioned manufacturability problem and achieves high levels of heat resistance and mechanical properties. So, it's preferable. On the other hand, it is also preferable that the base rubber (remainder) used in step (b) contains an ethylene copolymer resin. This increases the compatibility between the silane masterbatch and the catalyst masterbatch, and improves heat resistance and mechanical properties.

Although a part of the inorganic filler can be used in step (b), it is preferable in step (a) because a crosslinked structure involving the inorganic filler can be constructed to achieve higher levels of both heat resistance and mechanical properties. It is preferable to use When using an inorganic filler in step (b), the amount used is not particularly limited and is determined as appropriate.

Various additives may be mixed in either step (a) or step (b).
The antioxidant may be mixed in either step (a) or step (b), but mixing in step (b) makes the grafting reaction in step (a) more efficient. This is preferable in that it can be advanced.

The amount of organic peroxide mixed in step (a) is 0.01 to 0.6 parts by mass based on 100 parts by mass of the base rubber. When organic peroxide is mixed in the above content with millable silicone rubber containing the above content, competitive reactions (parallel reactions, side reactions) including crosslinking reactions between the millable silicone rubbers occur during melt mixing. In addition, it is possible to preferentially and selectively cause (promote) the grafting reaction of the silane coupling agent to the millable silicone rubber while suppressing the generation of gel particles. As a result, the appearance, heat resistance, and mechanical properties of the silane-crosslinked silicone rubber molded article can be achieved in a well-balanced manner. The amount of organic peroxide mixed is preferably 0.05 to 0.2 parts by mass.

<Step (a)>
Step (a) involves grafting a base rubber and a silane coupling agent in the presence of an inorganic filler to produce a silane masterbatch (containing a silane crosslinkable silicone rubber in which a silane coupling agent is grafted to a base rubber). This is a step of preparing silane MB).
In this step, the base rubber is heated and mixed with an inorganic filler and a silane coupling agent in the presence of an organic peroxide at a temperature equal to or higher than the decomposition temperature of the organic peroxide. Silane MB is thereby obtained as a molten mixture.

In step (a), the mixing temperature at which the above-mentioned components are melt-mixed (also referred to as melt-kneading) is equal to or higher than the decomposition temperature of the organic peroxide, preferably the decomposition temperature of the organic peroxide + (25 to 110)°C. The temperature is preferably 150 to 230°C, and even more preferably 175 to 210°C. Mixing conditions such as mixing time can be set as appropriate. For example, the mixing time can be 1 to 25 minutes, preferably 3 to 20 minutes. By melting and mixing at a temperature equal to or higher than the decomposition temperature of the organic peroxide, the organic peroxide is thermally decomposed to generate radicals, thereby progressing the grafting reaction.

As a mixing method, any method commonly used for mixing rubber, plastics, etc. may be used. As the mixing device, for example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, or various kneaders can be used, and a closed mixer such as a Banbury mixer or various kneaders is preferable.

In the present invention, the order of mixing is not specified, and the above components may be mixed in any order. For example, the components described above can be melt-mixed all at once.
In the production method of the present invention, step (a) is preferably mixed in the following steps (a-1) and (a-2) in the following mixing order.

Step (a-1): A step of mixing an inorganic filler and a silane coupling agent to prepare a mixture.
Processing step (a-2): The mixture obtained in step (a-1) and all or part of the base rubber,
Dissolves in the presence of organic peroxide at a temperature above the decomposition temperature of the organic peroxide.
Melt mixing process

In step (a-1), by premixing the inorganic filler and the silane coupling agent, the silane coupling agent is bonded or adsorbed to the inorganic filler with a weak bond, and the silane cup is bonded or adsorbed with a strong bond to the inorganic filler. It is possible to form a ring agent in a well-balanced manner. This effectively prevents volatilization of the silane coupling agent and further condensation reaction between unadsorbed silane coupling agents during melt mixing in step (a-2). As a result, it is possible to produce a silane-crosslinked silicone rubber molded article that exhibits a more excellent appearance and has further improved mechanical properties (tensile strength) and heat resistance due to the silane crosslinking method. Here, examples of the weak bond with the inorganic filler include interactions due to hydrogen bonds, interactions between ions, partial charges or dipoles, and effects due to adsorption. In addition, examples of the strong bond with the inorganic filler include a chemical bond with a site on the surface of the inorganic filler that can be chemically bonded.

The mixing method and mixing conditions in step (a-1) are not particularly limited, but using a known mixer, kneader, etc., the temperature is usually lower than the decomposition temperature of the organic peroxide, preferably 10 to 60°C. More preferably, methods and conditions include dry or wet mixing at around room temperature (20 to 25° C.) for several minutes to several hours. Among these, dry mixing (dry blending) is preferably performed at a temperature lower than the decomposition temperature of the organic peroxide. Other conditions for dry mixing are determined as appropriate.

In step (a-1), a base rubber may be mixed as long as the temperature is maintained below the above decomposition temperature.
The organic peroxide only needs to be present during the melt mixing in step (a-2), and may be mixed in step (a-2), but it may not be mixed in step (a-1). is preferred.

Next, the mixture obtained in step (a-1) and all or part of the base rubber are melt-mixed in the presence of an organic peroxide at a temperature equal to or higher than the decomposition temperature of the organic peroxide, Silane MB is prepared (step (a-2)). In this way, a silane masterbatch containing silane crosslinkable silicone rubber is prepared. In the melt mixing in this step, excessive crosslinking reaction (occurrence of gel lumps) between the base rubbers can be prevented while suppressing volatilization and self-condensation of the above-mentioned silane coupling agent.
The melt mixing method and conditions of this step (a-2) are not particularly limited, and the melt mixing method and conditions of the above step (a) can be applied.

In the melt mixing of step (a) and step (a-2), radicals generated from the organic peroxide cause silane cup formation of the millable silicone rubber, rather than competitive reactions including crosslinking reactions between the millable silicone rubbers. The grafting reaction of the ring agent occurs preferentially and selectively. Although the details of the reason are not yet clear, it is thought to be as follows. The content of vinyl groups in millable silicone rubber is usually not high, so there are few reaction points, and crosslinking reactions between millable silicone rubbers are difficult to occur. On the other hand, the silane coupling agent has a relatively small molecular weight, so the number of molecules per 1 part by mass is large, and it has a high degree of freedom in the molten mixture. The chance of reaction with rubber increases. Therefore, it is thought that the grafting reaction of the silane coupling agent occurs preferentially than the crosslinking reaction between the millable silicone rubbers. In addition, since ethylene copolymer resins and fluororubbers are thought to have lower radical-induced addition reactivity than silicone rubber, crosslinking reactions between ethylene copolymer resins or between fluororubbers, ethylene copolymer resins, fluororubbers, etc. It is considered that neither competitive reactions such as crosslinking reactions between different components of the millable silicone rubber nor grafting reactions of the silane coupling agent to the ethylene copolymer resin and fluororubber occur preferentially.

In step (a) and step (a-2), at least the following are possible modes in which the silane coupling agent undergoes a grafting reaction with the base rubber. In other words, the silane coupling agent weakly bonded or adsorbed to the inorganic filler is detached from the inorganic filler and undergoes a grafting reaction to the base rubber. The crosslinked structure formed in step (3) described later from this embodiment does not incorporate an inorganic filler, and is usually a crosslinked structure via a silanol condensate of silane coupling agents. Furthermore, the silane coupling agent that has been strongly bonded or adsorbed to the inorganic filler undergoes a grafting reaction to the resin while maintaining the bond or adsorption to the inorganic filler. The crosslinked structure formed in step (3) described later from this embodiment incorporates an inorganic filler, and becomes a crosslinked structure starting from the inorganic filler and via the silane coupling agent bonded thereto. By coexisting the crosslinked structures in both of the above embodiments, it is possible to construct a highly developed crosslinked structure including a crosslinked structure in which an inorganic filler is involved in a silane crosslinked silicone rubber molded article.

In step (a), antioxidants, additives, etc. can also be mixed. However, in step (a), it is preferable that the silanol condensation catalyst is not substantially mixed. Thereby, the occurrence of silanol condensation reaction of the silane coupling agent can be suppressed. In the present invention, "substantially not mixed" does not exclude the unavoidably present silanol condensation catalyst, but falls within a range that can suppress the silanol condensation reaction, for example 0. This means that it may be present as long as it is within a range of 0.01 parts by mass or less.

The silane MB prepared in step (a) contains a reaction mixture of a base rubber, an inorganic filler, and a silane coupling agent, and the silane coupling agent is mixed with the base rubber to the extent that it can be molded in step (b) described below. Contains silane-crosslinkable silicone rubber (silane graft polymer) grafted onto. The silane coupling agent grafted to the base rubber includes one bound to or adsorbed to the inorganic filler at its reaction site capable of silanol condensation.
Silane MB may be in the form of clay, pellets or powder.

<Step (b)>
In the production method of the present invention, a catalyst masterbatch (catalyst MB) is prepared by melt-mixing the remainder of the base rubber and a silanol condensation catalyst.
The melt mixing method and conditions in step (b) are not particularly limited, and the melt mixing method and conditions in step (a) above can be applied. For example, the melt mixing temperature may be at least the melting temperature of the base rubber, preferably 120 to 200°C, more preferably 140 to 180°C.
Catalyst MB may be in the form of clay, pellets or powder.

<Step (c)>
In the production method of the present invention, the silane masterbatch and the silanol condensation catalyst or catalyst masterbatch are then mixed.
The mixing in step (c) is not particularly limited, and an appropriate mixing method can be adopted in consideration of the characteristics (clay-like) of the silane MB and the catalyst MB. Examples include a mixing method (kneading) in which the materials are mixed using a roll or the like under non-high temperature conditions, a mixing method at a temperature at which at least the base rubber melts (melt mixing), and the like. The mixing method and conditions for kneading include, for example, a method and conditions in which the mixing method and conditions in step (a-1) are applied using a roll kneader or the like. On the other hand, the mixing method and conditions for melt mixing include, for example, basically the same method and conditions as the melt mixing in step (a). In this melt mixing, for example, the mixing temperature is appropriately selected depending on the base rubber, and is preferably 80 to 250°C, more preferably 100 to 240°C, and even more preferably 120 to 200°C. In the melt mixing step (c), a melt mixing method and conditions are set that can maintain the fluidity (moldability) of the silane crosslinkable silicone rubber composition. The silane crosslinkable silicone rubber in the silane crosslinkable silicone rubber composition is an uncrosslinked product in which the silane coupling agent is not subjected to silanol condensation. In practice, when melt-mixing is performed in step (c), some crosslinking (partial crosslinking) may be unavoidable, but the moldability of the resulting silane crosslinkable silicone rubber composition is maintained. For example, in order to avoid the occurrence or progress of a silanol condensation reaction, it is preferable that the mixed state of silane MB and silanol condensation catalyst is not kept at a high temperature for a long time.
In step (c), it is preferable to dry blend the silane MB and the silanol condensation catalyst or catalyst masterbatch before mixing them. The dry blending method and conditions are not particularly limited, and include, for example, the dry blending in step (a-1) and its conditions.

In this way, the silane crosslinkable silicone rubber composition of the present invention is produced as a mixture (kneaded product or molten mixture).
This silane crosslinkable silicone rubber composition contains the above-mentioned silane crosslinkable silicone rubber, an inorganic filler, a silanol condensation catalyst, and the like. In this silane crosslinkable silicone rubber, the reaction site of the silane coupling agent capable of silanol condensation may be bonded to or adsorbed to the inorganic filler, but does not undergo silanol condensation. Therefore, silane crosslinkable silicone rubber is based on a silane crosslinkable silicone rubber in which a silane coupling agent bonded or adsorbed with an inorganic filler is grafted onto a base rubber, and a silane coupling agent that is not bonded or adsorbed with an inorganic filler. silane crosslinkable silicone rubber grafted onto the rubber.
In addition to the above components, the silane crosslinkable silicone rubber composition may contain components based on various competitive reactions depending on the selectivity of the grafting reaction of the silane coupling agent. Such components include, for example, cross-linked bodies of organopolysiloxanes, cross-linked bodies of fluororubbers, cross-linked bodies of different types of millable silicone rubber and fluororubber, and grafting bonds of silane coupling agents. Examples include fluororubber. In addition, when the base rubber contains an ethylene copolymer resin, the silane crosslinkable silicone rubber composition includes, in addition to the above components, a crosslinked product of ethylene copolymer resins, and a heterogeneous component containing an ethylene copolymer resin. The crosslinked product may also contain an ethylene copolymer resin or the like to which a silane coupling agent is grafted.

<Step (2)>
In the method for producing a silane-crosslinked silicone rubber molded article of the present invention, the silane-crosslinked silicone rubber composition is then molded to obtain a molded article.
The molding method is not particularly limited, and can be appropriately selected depending on the characteristics of the silane crosslinkable silicone rubber composition and the form of the intended product. Examples of the molding method include press molding, molding using other general-purpose molding machines, and extrusion molding using a silicone rubber-dedicated or general-purpose extruder or injection molding machine. When manufacturing wiring materials, extrusion molding is preferred in terms of productivity and the ability to co-extrude with conductors. When the masterbatch is a clay-like solid and the silane crosslinkable silicone rubber composition is a kneaded product, press molding, extrusion molding using an extruder or injection molding machine dedicated to silicone rubber, etc. are preferable. When the rubber composition is a molten mixture, molding using a general-purpose molding machine, extrusion molding using a general-purpose extruder or injection molding machine, etc. are preferred.
In step (2), depending on the molding method, the silane crosslinkable silicone rubber composition can be molded as it is, or it can be melt-mixed and then molded. For example, when using press molding, etc., the silane crosslinkable silicone rubber composition can be pressed and molded as it is, and when using extrusion molding, etc., the silane crosslinkable silicone rubber composition can be melt-mixed and molded. be able to.
The molding conditions are not particularly limited as long as the silane crosslinkable silicone rubber composition of the present invention can be molded and the silanol condensation reaction does not occur. Further, the melt mixing conditions are not particularly limited as long as the silane crosslinkable silicone rubber composition of the present invention can be uniformly mixed and molded and the silanol condensation reaction does not occur. As both conditions, for example, the melt mixing method and conditions of step (a) can be applied. More specifically, the molding (melt mixing) temperature in this step is set to be higher than the temperature at which the base rubber melts, preferably from 80 to 250°C, more preferably from 100 to 240°C, even more preferably from 120 to 200°C. In this melt mixing, the melt mixing method and conditions are set while maintaining the moldability of the molten mixture of the silane crosslinkable silicone rubber composition. When coextruding with a conductor using an extrusion molding machine, the temperature of the cylinder part should be about 120 to 180°C, and the temperature of the crosshead part should be about 160 to 200°C, depending on various conditions such as the take-up speed of the conductor etc. It is preferable to set it to . The molding speed (linear speed) in extrusion molding is not particularly limited, and can be appropriately set depending on the characteristics or performance of the extruder, the extrusion amount (coating amount), and the like. The linear speed can be generally set at 1 to less than 20 m/min, preferably 1 to 10 mm/min. This linear speed can be suitably applied to the extruder used in the examples described later and the amount of extrusion (coating thickness) to the outer circumferential surface of the conductor.
The silane crosslinkable silicone rubber in the molded product obtained in step (2) is an uncrosslinked product in which the silane coupling agent is not subjected to silanol condensation. Practically speaking, when melt-mixing is performed in step (2), partial crosslinking (partial crosslinking) is unavoidable, but the moldability of the resulting molded product is maintained. For example, in order to avoid the occurrence or progression of a silanol condensation reaction, it is preferable that the silane crosslinkable silicone rubber composition is not kept at a high temperature for a long period of time.

Step (2) can be performed simultaneously or consecutively with step (c). For example, silane MB and catalyst MB are mixed by dry blending or the like immediately before or within a coating device (extruder), and then melt-mixed in the coating device (step (c)) to coat the outer peripheral surface of a conductor, etc. A series of steps of (coextrusion) molding (step (2)) can be adopted. Alternatively, a series of steps can be adopted in which silane MB and catalyst MB are kneaded (step (c)) and then molded using a molding machine such as a press (step (2)).

<Step (3)>
In the method for producing a silane-crosslinked silicone rubber molded article of the present invention, the molded article obtained in step (2) is then brought into contact with water to produce a silane-crosslinked silicone rubber molded article. Since the molded body obtained in step (2) is an uncrosslinked body, in this step, a silanol condensation reaction is caused at the reaction site capable of silanol condensation of the silane coupling agent grafted to the base rubber, This is allowed to progress (promote) to finally cause silane crosslinking.
The uncrosslinked molded body can be brought into contact with water by a conventional method. The silanol condensation reaction proceeds even if it is left standing at room temperature, for example, about 20 to 25° C., but it is preferable to actively bring it into contact with water to promote the silanol condensation reaction (crosslinking reaction). Examples of the contact method include methods (conditions) normally applied to silane crosslinking methods, such as immersion in hot water, placing in a moist heat tank, and exposure to high-temperature steam. .

In this way, the silane-crosslinked silicone rubber molded article of the present invention is produced.
This silane crosslinked silicone rubber molded article contains a crosslinked silicone rubber in which a base rubber (particularly organopolysiloxane contained in a millable silicone rubber) is condensed via a siloxane bond. Further, the silane crosslinked silicone rubber molded article contains an inorganic filler, and this inorganic filler may be bonded to the silane coupling agent of the crosslinked silicone rubber. Therefore, a crosslinked silicone rubber is a crosslinked silicone rubber in which multiple base rubbers are bonded or adsorbed to an inorganic filler using a silane coupling agent, and are bonded (crosslinked) via the inorganic filler and the silane coupling agent, and a grafted silicone rubber to the base rubber. Crosslinked silicone that is crosslinked via the silane coupling agent (siloxane bond) (without an inorganic filler) by hydrolyzing the hydrolyzable groups of the silane coupling agent that are bonded to each other and causing a silanol condensation reaction with each other. It is thought to contain rubber.
Note that the silane-crosslinked silicone rubber molded article of the present invention may contain a component based on the above-mentioned competitive reaction, and a silanol condensate.

As described above, in step (a), the production method of the present invention carries out the grafting reaction between the silane coupling agent and the base rubber in the presence of an inorganic filler, and furthermore, the silane coupling agent undergoes volatilization and self-condensation. Reactions, and even competitive reactions including crosslinking reactions between organopolysiloxanes, can be suppressed and caused (promoted). Furthermore, when the base resin contains an ethylene copolymer resin, the resin has high fluidity during molding, and can be molded using a general-purpose extrusion molding machine without sacrificing excellent manufacturability. Therefore, when the silane crosslinkable silicone rubber composition of the present invention is brought into contact with water under relatively mild conditions, it is possible to construct a highly developed crosslinked structure including a crosslinked structure involving an inorganic filler. It is possible to produce a silane-crosslinked silicone rubber molded product that has a beautiful appearance and exhibits remarkable heat resistance and tensile strength.

[Silane crosslinked silicone rubber molded product]
The silane-crosslinked silicone rubber molded product of the present invention is a product containing the silane-crosslinked silicone rubber molded product of the present invention, and can be used as various rubber molded products, preferably as a substitute for conventional silicone rubber molded products. be able to. Examples include coating materials for wiring materials such as insulated wires, cables, and optical fiber cables, materials for rubber substitute wires and cables, heat-resistant parts for microwave ovens or gas ranges, heat-resistant wire parts, heat-resistant sheets, heat-resistant films, and the like. In addition, power plugs, connectors, sleeves, boxes, tape base materials, tubes, sheets, packing, cushioning materials, earthquake-proofing materials, wiring materials used for internal and external wiring of electrical and electronic equipment, especially electric wires and optical fiber cables, Further examples include the above-mentioned wiring materials and tubular molded bodies.
The silane crosslinked silicone rubber molded article of the present invention may be a molded article containing the silane crosslinked silicone rubber molded article of the present invention in a part (rubber molded part), and the silane crosslinked silicone rubber molded article of the present invention It may also be a molded product consisting only of the body.
Similar to the silane crosslinked silicone rubber molded article of the present invention, the silane crosslinked silicone rubber molded article of the present invention can achieve high heat resistance and strength while maintaining an excellent appearance. Therefore, the silane-crosslinked silicone rubber molded product of the present invention can be used as a coating material for wiring materials, sheets, packing, and even for applications that require a high degree of heat resistance, such as around engine compartments of automobiles, by utilizing the above characteristics. , packing around high-output motors, and other applications that are difficult to apply with general silicone rubber, such as those easily damaged by repeated vibrations, bending and stretching, etc. It is preferable to apply the present invention to applications in which the process is repeated, such as insulated wires for automobiles, wiring materials for industrial robots, and industrial wires that are dragged around outdoors.

A sheet or packing that is preferable as the silane-crosslinked silicone rubber molded product of the present invention will be explained.
Examples of the sheet or packing include those obtained by molding the silane crosslinkable silicone rubber composition of the present invention into a predetermined shape and then contacting it with water to crosslink it. The shape and dimensions of the sheet or packing are appropriately determined depending on the application and the like.

A preferred wiring material (insulated electric wire for automobiles) as the silane-crosslinked silicone rubber molded product of the present invention will be described.
The wiring material is a wiring material having a coating layer around the outer periphery of the conductor, and this coating layer is formed by molding the silane crosslinkable silicone rubber composition of the present invention into a tubular layer and crosslinking it to form the silane crosslinkable silicone rubber composition of the present invention. Examples include wiring materials formed from silicone rubber molded bodies.
The wiring material is the same as the usual one used in various electric/electronic equipment fields and industrial fields, except that the coating layer is formed of the silane crosslinked silicone rubber molded product of the present invention. The coating layer formed of the silane-crosslinked silicone rubber molded product of the present invention is provided on the outer circumferential surface of the conductor directly or via another layer, and may be coated with other layers depending on the type, application, required characteristics, etc. of the wiring material. The presence or absence of the material, the material, etc. are determined as appropriate. As the conductor, ordinary conductors can be used, such as copper or aluminum single wires or stranded wires (those made by longitudinally splicing or twisting tensile strength fibers). In addition to bare wires, tin-plated wires or wires with an enamel-covered insulating layer can also be used. The thickness of the coating layer formed from the silane-crosslinked silicone rubber molded article of the present invention is not particularly limited, but is usually about 0.15 to 5 mm.
The wiring material of the present invention can be manufactured by various molding methods in step (2), for example, by molding with an extruder or injection molding machine and then contacting with water. Preferably, it can be manufactured by arranging the silane crosslinkable silicone rubber composition of the present invention in a tubular shape around the outer periphery of a conductor and then subjecting it to a crosslinking reaction (silanol condensation reaction). For example, in the above-mentioned method for producing a silane-crosslinked silicone rubber molded article of the present invention, the molding step (2) is carried out using a coating device (extruder) dedicated to silicone rubber or a general-purpose coating device (extruder) to coat the silane-crosslinkable silicone rubber composition. It can be manufactured by coextruding the outer periphery of the conductor. The specific coextrusion molding is as described above.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited thereto.

Compounds used in Examples and Comparative Examples are shown below.
<Base rubber>
(1) Millable silicone rubber: ELASTSIL R401/40S (trade name, compound containing methyl vinyl silicone rubber and fumed silica (A agent), specific gravity 1.12 g/cm ³ , manufactured by Asahi Kasei Wacker Co., Ltd.)
(2) Fluororubber: AFLAS400E (trade name, tetrafluoroethylene-propylene rubber, manufactured by AGC)
(3) Ethylene-ethyl acrylate copolymer resin (EEA): NUC6510 (trade name, manufactured by ENEOS NUC)
(4) Ethylene-vinyl acetate copolymer resin (EVA): VF120T (trade name, manufactured by Ube Maruzen Polyethylene Co., Ltd.)
(5) Linear low-density polyethylene (LLDPE): Evolue SP0510 (trade name, manufactured by Prime Polymer Co., Ltd.)
(6) Polypropylene resin (PP): PB222A (trade name, Random PP, manufactured by Sun Allomer Co., Ltd.)

The specific gravity of the millable silicone rubber is a value measured in accordance with JIS K 7112 (1999) method A (underwater displacement method).
Specifically, a 20 mm square (cubic) sample was prepared from each millable silicone rubber, and its mass was measured in the air and in liquid (distilled water). The value ρ calculated from the following formula from the obtained value and the density (specific gravity) of the liquid was taken as the specific gravity of the millable silicone rubber.

ρ={Ma/Ma-Mw}×ρw

In the above formula, Ma represents the mass of the sample in the atmosphere (g), Mw represents the mass of the sample in the liquid (g), and ρw represents the density of the liquid (g/cm ³ ).

<Inorganic filler>
(1) Inorganic filler: Softon 1200 (trade name, calcium carbonate, manufactured by Bihoku Funka Kogyo Co., Ltd.)
(2) Inorganic filler: Aerosil 200 (trade name, dry silica, manufactured by Nippon Aerosil Co., Ltd.)
(3) Inorganic filler: Crystallite 5X (trade name, crystalline silica, manufactured by Takimorisha)

<Silane coupling agent>
KBM-1003: Trade name, vinyltrimethoxylan, manufactured by Shin-Etsu Chemical <Silanol condensation catalyst>
ADEKA STAB OT-1: Trade name, dioctyltin dilaurylate, manufactured by ADEKA <Organic peroxide>
Perhexa 25B: trade name, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, decomposition temperature 154°C, manufactured by NOF Corporation

<Antioxidant>
Irganox 1010: Product name, hindered phenolic antioxidant, manufactured by BASF ADEKA STAB CDA-10: Product name, hydrazine-based heavy metal deactivator, manufactured by ADEKA

(Examples 1 to 17 and Comparative Examples 2 to 6)
Examples 1 to 17 and Comparative Examples 2 to 6 were carried out using the components shown in Tables 1 to 3, respectively.
In Tables 1 to 3, the numerical values regarding the amount (content) of each example represent parts by mass unless otherwise specified. Further, for each component, a blank column means that the amount of the corresponding component is 0 parts by mass.
In each Example and Comparative Example, a part of the base rubber (specifically, millable silicone rubber or EEA shown in the "Catalyst MB" column of Tables 1 to 3) was added to the catalyst MB at the mass ratio shown in the same column. It was used as a carrier resin.

First, the inorganic filler, silane coupling agent, and organic peroxide are put into a rotary blade mixer (Mazeler PM: trade name, manufactured by Maseller) at the mass ratio shown in the "Silane MB" column of Tables 1 to 3. The mixture was stirred (premixed) for 1 minute at room temperature (25° C.) at a rotational speed of 10 rpm (step (a-1)). A powder mixture was thus obtained.
Next, the powder mixture and the base rubber and antioxidant shown in the "Silane MB" column of Tables 1 to 3 were mixed in the mass ratio shown in the same column in a Banbury mixer (capacity 2 L) heated to 80°C in advance. After mixing for 5 minutes at a rotation speed of 40 rpm, finishing kneading (melt mixing) was further performed for 3 minutes at a rotation speed of 30 rpm. After confirming that the temperature of the mixture has reached 180 to 200 ° C., which is higher than the decomposition temperature of the organic peroxide, the molten mixture is rolled out to a thickness of about 3 mm with an 8-inch open roll, and pelletized using a square pelletizer. Silane MB was obtained (step (a) together with step (a-2) and step (a-1)).
In addition, since the silane MB of Example 1, Comparative Example 2, Comparative Example 5, and Comparative Example 6 could not be pelletized, the silane MB discharged from the Banbury mixer was used as the silane MB.

Meanwhile, the base rubber, silanol condensation catalyst, and antioxidant shown in the "Catalyst MB" column of Tables 1 to 3 were added to a Banbury mixer (capacity 2 L) heated to 80°C in advance at the mass ratio shown in the same column. After adding them one after another and mixing for 5 minutes at a rotation speed of 40 rpm, finishing kneading (melt mixing) was performed for 3 minutes at a rotation speed of 30 rpm. After confirming that the temperature of the mixture reached about 160 ° C. and that the carrier rubber was sufficiently melted, the molten mixture was rolled to a thickness of about 3 mm using an 8-inch open roll and pelletized using a square pelletizer to obtain catalyst MB. (Step (b)).
In addition, since the catalyst MB of Example 1 could not be pelletized, the catalyst MB discharged from the Banbury mixer was used as the catalyst MB.

- Production of sheet-shaped molded bodies -
The prepared silane MB and catalyst MB were kneaded for 5 minutes at room temperature (25° C.) using an 8-inch open roll to obtain a silane crosslinkable silicone rubber composition (step (c)). At this time, the mixing ratio of silane MB and catalyst MB was the mass ratio shown in the "silane MB" column and "catalyst MB" column in Tables 1 to 3.
Next, using each of the prepared silane crosslinkable silicone rubber compositions, a sheet-like molded article having an A4 size (210 mm x 297 mm) and a thickness of 2 mm was manufactured in the following manner. That is, after the prepared silane crosslinkable silicone rubber composition was put into a press that had not been preheated, heating was started. When the temperature of the silane crosslinkable silicone rubber composition reached 120° C., it was pressed under a pressure of 10 MPa, and this state was maintained for 3 minutes to perform press molding (step (2)).
The obtained sheet-like molded body (thickness: 2 mm) was left standing in an atmosphere of a temperature of 60° C. and a humidity of 95% RH for 24 hours to bring the silane crosslinkable silicone rubber composition into contact with water (step (3) ).
In this way, sheet-like molded bodies (corresponding to crosslinked bodies and silane crosslinked silicone rubber molded bodies) each having a thickness of 2 mm were produced.

- Manufacturing of insulated wires -
The prepared silane MB and catalyst MB were put into a plastic bag at the mass ratio shown in the "Silane MB" column and "Catalyst MB" column in Tables 1 to 3, and dry blended for 3 minutes at room temperature (25 ° C.). A dry blend was obtained.
Next, the obtained dry blend was introduced into an extruder (cylinder part temperature: 130°C, crosshead part temperature: 180°C) equipped with a screw having L/D=25 and a screw diameter of 25 mm. This extruder is a general-purpose plastic extrusion molding machine (model number: D2-1429, manufactured by Omiya Seiki Co., Ltd.). While melt-mixing the dry blend in the extruder (step (c)), the silane crosslinkable silicone rubber composition is applied to a thickness of 0.8 mm on the outer peripheral surface of a copper conductor with a diameter of 0.8 mm at a linear speed of 10 m/min. A coated conductor with an outer diameter of 2.4 mm was obtained by extrusion coating with a thickness of 8 mm (step (2)). This coated conductor was left in an atmosphere with a temperature of 60° C. and a humidity of 95% for 24 hours to contact with water (step (3)).
In this way, insulated wires each having a coating layer made of a silane crosslinked silicone rubber molded product on the outer peripheral surface of the conductor were manufactured.
In addition, in Example 1, Comparative Example 2, Comparative Example 5, and Comparative Example 6, insulated wires were not manufactured because the crosslinkable silicone rubber composition could not be extruded.

(Comparative example 1)
Each component shown in the "Silane MB" column of Table 3 was put into a Banbury mixer, melted and mixed at 60 to 100°C for 10 minutes, then discharged at a material discharge temperature of 100°C, and thinned to about 3 mm with an 8-inch open roll. After stretching, an attempt was made to obtain a crosslinkable silicone rubber composition in the form of pellets using a square pelletizer, but the composition could not be pelletized.
Using the prepared crosslinkable silicone rubber composition, press molding was performed in the same manner as in Example 1 to produce a sheet-like molded product with a thickness of 2 mm.
In addition, since the crosslinkable silicone rubber composition of Comparative Example 1 could not be extruded, no insulated wire was manufactured.

The produced insulated wires or sheet-like molded bodies were evaluated as follows, and the results are shown in Tables 1 to 3.
Note that a blank column in the tensile test column of each table indicates that the tensile test was not conducted using the corresponding test piece.

<Sheet appearance test>
The appearance of each produced sheet-like molded product was visually confirmed and evaluated using the following evaluation criteria.

- Evaluation criteria -
"A" (good appearance, passed): The appearance (surface) was smooth and no gel spots were observed. "B" (acceptable appearance, passed): 1 to 10 gel spots of 1 mm or less were observed on the sheet surface. "D" (poor appearance, rejected): If significant flow marks, gel spots, roughness, etc. are observed on the surface.

<Hot set test>
A No. 3 dumbbell-shaped test piece as specified in JIS K 6251 (2017) was punched out from each of the produced sheet-like molded bodies. A weight of 205 gf (20 N/cm ² ) was attached to the lower end of this dumbbell test piece, and the test piece was hung vertically and left in a temperature environment of 150° C., 200° C., or 250° C. for 15 minutes.
After 15 minutes, the gage length of each test piece was measured with the weight attached. At this time, the part between the gauge marks of the test piece was not cut, and the gauge length of the test piece was within 175% of that before the test (before load application: initial gauge length) (the gauge length was 2.75%). If the growth rate is less than 20%, it is considered a pass. The results of the hot set test were evaluated by applying them to the following evaluation criteria.
This test is a test to evaluate the heat resistance of the test piece, and also a test to evaluate the crosslinking state of the test piece. The higher the evaluation standard of this test, the more a sufficient crosslinked structure has been built in the test piece, which means that it exhibits high heat resistance and does not melt even at high temperatures.

- Evaluation criteria -
"A" (excellent, passed): Passed at a temperature of 250°C "B" (good, passed): Failed at a temperature of 250°C but passed at a temperature of 200°C "C" ( Acceptable, Pass): Those that failed at a temperature of 200°C but passed at a temperature of 150°C “D” (Fail): Those that did not pass at any temperature

<Tensile test>
A conductor was pulled out from each of the manufactured insulated wires to prepare a tubular test piece made of a silane-crosslinked silicone rubber molded body.
On the other hand, for Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 5, Comparative Example 6, and Example 2, in which insulated wires could not be manufactured, JIS K 6251 (2017 ) A dumbbell test piece was prepared by punching out a test piece in the shape of a No. 3 dumbbell.
Using each of the prepared test pieces, a tensile test was conducted in accordance with JIS C 3005 under the conditions of a gauge distance of 20 mm and a speed of 200 mm/min, and the strength at break (MPa) and elongation at break ( %) was measured.
The measured strength at break (tensile strength) and elongation at break (elongation at break) were evaluated using the following evaluation criteria. Of this test, elongation at break is a reference test.

- Tensile strength evaluation criteria -
"A" (excellent, pass): 12 MPa or more "B" (good, pass): 8 MPa or more, less than 12 MPa "C" (acceptable, pass): 4.5 MPa or more, less than 8 MPa "D" (Fail): Less than 4.5 MPa

- Evaluation criteria for elongation at break -
"A" (excellent, pass): 400% or more "B" (good, pass): 250% or more, less than 400% "C" (acceptable, pass): 150% or more, less than 250% "D" (fail): less than 150%

<Heat aging test>
The tubular test piece or each dumbbell test piece prepared in the above <Tensile Test> was subjected to aging treatment by being held at a temperature of 200° C. for 168 hours.
For each test piece after the aging treatment, the elongation at break was measured under the same conditions as in the above <Tensile test>.
The residual elongation at break (%) was calculated by dividing the elongation at break after the aging treatment by the elongation at break before the aging treatment (the elongation at break obtained in the above <Tensile Test>).
The obtained residual elongation at break was evaluated using the following evaluation criteria.
This test is a test to evaluate the heat resistance of the test piece.

- Evaluation criteria -
"A" (excellent, passed): 80% or more "B" (good, passed): 65% or more, less than 80% "C" (pass): 50% or more, less than 65% "D" ( Fail): Less than 50%

<Moldability test: reference test>
In this test, in each Example and Comparative Example, we investigated whether the silane MB and catalyst MB could be prepared as pellets that are difficult to fuse (pellet preparation suitability), and further, using these pellets to manufacture the above insulated wire by extrusion molding. We evaluated whether it was possible or not.
Specifically, each of the silane MB pellets and the catalyst MB pellets prepared in each example and comparative example was held at a temperature of 40° C. for 24 hours. The condition of each pellet after being held for 24 hours was visually confirmed, and whether extrusion molding using the pellets was possible was evaluated by applying the following evaluation criteria. When the evaluation of pellet preparation suitability differed between silane MB and catalyst MB, the evaluation of the inferior one was adopted.

- Evaluation criteria -
"A" (excellent, passed): When the pellets do not fuse together (blocking) and there is no problem with extrusion molding (extrusion molding was possible) "D" (fail): Pelletization If extrusion molding is not possible due to

<Extrusion appearance test: reference test>
The appearance of each manufactured insulated wire was visually observed and evaluated using the following evaluation criteria.
In addition, the products that failed the above moldability test (Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 5, and Comparative Example 6) could not be extruded, so the results of the extrusion appearance test were evaluated. D”.

- Evaluation criteria -
"A" (advanced appearance, passed): The surface of the insulated wire was clean and no gel spots were observed. "B" (acceptable appearance, passed): The average number of gel spots on the surface of the insulated wire was 1 to 5 per 1 m. "D" (poor appearance, failure): If a large amount of gel or roughness is observed on the surface of the insulated wire, and the appearance of the insulated wire is defective.

The following can be seen from the results in Tables 1 to 3.
In Comparative Example 1, which employs the chemical crosslinking method, no crosslinking reaction occurs under the above press molding conditions, and the heat resistance (hot set test and heat aging test) and mechanical properties (tensile test) are inferior. When employing a chemical crosslinking method, heating at a high temperature for a long time is required to cause a crosslinking reaction, which results in poor manufacturability in terms of productivity and production cost.
Even if the silane crosslinking method is applied, Comparative Example 2, which contains millable silicone rubber and ethylene copolymer resin as the base resin but does not contain fluororubber, is inferior in strength.
Comparative Examples 3 and 4, in which the content of the inorganic filler is not within the range defined by the present invention, cannot achieve both high levels of heat resistance and tensile strength. That is, Comparative Example 3, in which the content is too low, is inferior in heat resistance (hot set test) and tensile strength, and Comparative Example 4, in which the content is too high, is inferior in heat resistance (heat aging test).
Furthermore, in Comparative Example 5, in which the amount of the silanol condensation catalyst blended is too small, the silanol condensation reaction cannot be promoted and the crosslinked structure itself is not sufficiently constructed, resulting in poor heat resistance and tensile strength. On the other hand, Comparative Example 6, which contains too much silanol condensation catalyst, is inferior in appearance and elongation at break.

On the other hand, Examples 1 to 17 in which a specific amount of silane coupling agent was used in the coexistence of a specific amount of silanol condensation catalyst and an inorganic filler in addition to using fluororubber for millable silicone rubber In both cases, the silane crosslinking reaction can be caused (promoted) under mild conditions without the need for special crosslinking equipment such as chemical crosslinking tubes or electron beam crosslinking machines, and molded products with excellent appearance can be produced. I can do it. In addition, the molded product exhibits extremely high heat resistance and excellent tensile strength, with a residual elongation at break of 50% or more even after being held at 200° C. for 168 hours. That is, it can be seen that the silane-crosslinked silicone rubber composition of the present invention can produce a silane-crosslinked silicone rubber molded article with excellent appearance and high heat resistance and strength with excellent manufacturability.
In addition, when ethylene copolymer resin is used in combination with millable silicone rubber and fluororubber, even a general-purpose extruder can extrude a silane-crosslinked silicone rubber molded product that exhibits excellent appearance, high heat resistance, and strength. Can be molded.

Claims (9)

For 100 parts by mass of a base rubber containing millable silicone rubber and fluororubber, 1 to 15 parts by mass of a silane coupling agent grafted to the base rubber and 0.5 to 100 parts by mass of an inorganic filler, A silane crosslinkable silicone rubber composition containing 0.01 to 0.5 parts by mass of a silanol condensation catalyst. The silane crosslinkable silicone rubber composition according to claim 1, wherein the fluororubber comprises tetrafluoroethylene-propylene rubber. The silane crosslinkable silicone rubber composition according to claim 1 or 2, wherein the base rubber contains an ethylene copolymer resin. The silane crosslinkable silicone rubber composition according to any one of claims 1 to 3, wherein the inorganic filler is at least one selected from metal hydrates, talc, clay, silica, calcium carbonate, and carbon black. thing. The silane crosslinkable silicone rubber composition according to any one of claims 1 to 4, wherein the content of the silane coupling agent is 3 to 15 parts by mass based on 100 parts by mass of the base rubber. A silane-crosslinked silicone rubber molded article obtained by molding the silane-crosslinkable silicone rubber composition according to any one of claims 1 to 5 and then contacting it with water. A silane crosslinked silicone rubber molded article comprising the silane crosslinked silicone rubber molded article according to claim 6. For 100 parts by mass of a base rubber containing millable silicone rubber and fluororubber, 1 to 15 parts by mass of a silane coupling agent having a grafting reaction site capable of grafting to the base rubber, and 0.5 to 0.5 parts by mass of an inorganic filler. Step (1) of obtaining a silane crosslinkable silicone rubber composition by mixing 100 parts by mass, 0.01 to 0.6 parts by mass of an organic peroxide, and 0.01 to 0.5 parts by mass of a silanol condensation catalyst. ) A method for producing a silane crosslinkable silicone rubber composition, comprising:
The step (1) includes the following step (a) and step (c), provided that when a part of the base rubber is melt-mixed in the following step (a), the following step (a) and step ( A method for producing a silane crosslinkable silicone rubber composition, comprising b) and step (c).
Step (a): All or part of the base rubber, the silane coupling agent, and the
The inorganic filler and the organic peroxide are heated at a temperature below the decomposition temperature of the organic peroxide.
Step (b): melt-mixing the remainder of the base rubber and the silanol condensation catalyst at a temperature above to prepare a silane masterbatch.
Step (c) of preparing a medium masterbatch: the silane masterbatch and the silanol condensation catalyst or the catalyst masterbatch.
Process of mixing with starbatch A method for producing a silane-crosslinked silicone rubber molded article comprising the following steps (1), (2) and (3),
Step (1): 100 mass of base rubber containing millable silicone rubber and fluororubber
%, a grafting reaction part capable of grafting reaction to the base rubber
1 to 15 parts by mass of a silane coupling agent having 1 to 15 parts by mass, and 0.0 parts by mass of an inorganic filler.
5 to 100 parts by mass, 0.01 to 0.6 parts by mass of organic peroxide, and cyano
0.01 to 0.5 parts by mass of a silane-crosslinkable silica
Step (2): Molding the silane crosslinkable silicone rubber composition to obtain a molded article Step (3): Bringing the molded article into contact with water to obtain a silane crosslinked silicone rubber molded article Engineering
Step (1) includes the following step (a) and step (c), provided that in the case where a part of the base rubber is melt-mixed in the following step (a), the following step (a) and step A method for producing a silane-crosslinked silicone rubber molded article, comprising (b) and step (c).
Step (a): All or part of the base rubber, the silane coupling agent, and the
The inorganic filler and the organic peroxide are heated at a temperature below the decomposition temperature of the organic peroxide.
Step (b): melt-mixing the remainder of the base rubber and the silanol condensation catalyst at a temperature above to prepare a silane masterbatch.
Step (c) of preparing a medium masterbatch: the silane masterbatch and the silanol condensation catalyst or the catalyst masterbatch.
Process of mixing with starbatch