JP4367637B2 - Rubber molded product obtained by co-crosslinking perfluoropolyether-based fluorine-containing rubber composition and different rubber composition, and method for producing the same - Google Patents

Description

  The present invention relates to a rubber molded product obtained by integrally molding a perfluoropolyether-based fluororubber having good solvent resistance, chemical resistance, heat resistance, and low-temperature characteristics and another type of rubber by simultaneous crosslinking, and a method for producing the same.

  Conventional vinylidene fluoride-based fluororubber is an elastomer excellent in heat resistance, chemical resistance, mechanical strength, and the like, and is therefore industrially used in a wide range of fields mainly in the automobile and machine industries.

  However, its chemical resistance is inadequate and easily swells in polar solvents such as ketones, lower alcohols, carbonyls, organic acids, etc. There is a disadvantage that the elongation is extremely lowered. Further, in terms of low temperature characteristics, rubber elasticity is lost at −20 ° C. or lower and the seal material cannot be used. Therefore, there is a general limit to use in cold regions.

  Therefore, in order to improve these drawbacks, a liquid or millable type fluorinated curable composition mainly composed of a perfluoro compound and a fluorinated organohydrogenpolysiloxane has been proposed (Patent Documents 1 to 4: Japanese Patent No. 2990646 (Japanese Patent Laid-Open No. 8-199070), Japanese Patent Laid-Open No. 2000-007835, Japanese Patent Laid-Open No. 2001-106893, Japanese Patent Laid-Open No. 2003-201401).

［但し、式中Ｒ¹は置換又は非置換の一価炭化水素基、Ｒ²は水素原子又は置換又は非置換の一価炭化水素基、Ｑは下記一般式（２）又は下記一般式（３）で示される基であり、

（但し、式中Ｒ³は結合途中に酸素原子、窒素原子及びケイ素原子の１種又は２種以上を介在させてもよい置換又は非置換の二価炭化水素基を示す。）

（但し、式中Ｒ⁴及びＲ⁵はそれぞれ置換又は非置換の二価炭化水素基を示す。）
Ｒｆは二価のパーフルオロアルキレン基又は二価のパーフルオロポリエーテル基であり、ａは０以上の整数である。］ That is, in JP-A-8-199070 (Patent Document 1), (A) a fluorine-containing amide compound represented by the following general formula (1),

[Wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, Q is the following general formula (2) or the following general formula (3 )

(However, in the formula, R ³ represents a substituted or unsubstituted divalent hydrocarbon group in which one or more of an oxygen atom, a nitrogen atom and a silicon atom may be interposed in the middle of bonding.)

(In the formula, R ⁴ and R ⁵ each represent a substituted or unsubstituted divalent hydrocarbon group.)
Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and a is an integer of 0 or more. ]

  (B) one or more monovalent perfluorooxyalkyl groups, monovalent perfluoroalkyl groups, divalent perfluorooxyalkylene groups or divalent perfluoroalkylene groups in one molecule, and 2 A composition containing a fluorine-containing organohydrogensiloxane having at least one hydrosilyl group and (C) a catalytic amount of a platinum group compound, wherein the amount of the component (B) is an aliphatic unsaturated group 1 in the composition. Disclosed is a curable composition characterized in that the amount of hydrosilyl group (Si—H group) is 0.5 to 5 moles per mole.

  In addition, in Japanese Patent Application Laid-Open No. 2000-007835 (Patent Document 2), (A) a molecule having at least two alkenyl groups and a main chain having a divalent perfluoroalkylene structure or a divalent perfluoro group. A polymer in which a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule is added to a part of the alkenyl group of the perfluoro compound having a polyether structure, (B) a reinforcing filler, (C) A crosslinkable fluororubber composition comprising a sufficient amount of a crosslinking agent or peroxide crosslinking agent having a hydrosilyl group in the molecule to cure the component (A) Things are disclosed.

  In JP-A-2001-106893 (Patent Document 3), at least one (A) component, (B) component, and (C) component in the molecule as (D) component is the same as Patent Document 2 described above. A crosslinkable fluororubber composition comprising a surface treatment agent having a fluoroalkyl group or a fluoropolyalkyl ether group and one silanol group in the molecule is disclosed.

（但し、ｎは１以上の整数、Ｒｆは二価のパーフルオロアルキレン基又はパーフルオロオキシアルキレン基、Ｑは二価の有機基、Ｚは一価の有機基を示す。）
（Ｂ）補強性フィラー、（Ｃ）パーオキサイド架橋剤を含有してなることを特徴とする架橋性フッ素ゴム組成物が開示されている。 Further, in Japanese Patent Application Laid-Open No. 2003-201401 (Patent Document 4), (A) a polymer compound represented by the following general formula (4) having a viscosity at 25 ° C. of 1,000 Pa · s or more,

(However, n represents an integer of 1 or more, Rf represents a divalent perfluoroalkylene group or perfluorooxyalkylene group, Q represents a divalent organic group, and Z represents a monovalent organic group.)
A crosslinkable fluororubber composition comprising (B) a reinforcing filler and (C) a peroxide crosslinking agent is disclosed.

Here, in the above formula (4), Rf is a divalent perfluoroalkylene group represented by —C _m F _2m — (m = 2 to 15) or the following formulas (5), (6), (7) A divalent perfluorooxyalkylene group selected from the group represented by:

（Ｘはそれぞれ独立にＦ又はＣＦ₃基、ｒは２〜６の整数、ｔ、ｕはそれぞれ１又は２、ｐ、ｑはそれぞれ０〜２００の整数、ｓは０〜６の整数であるが、ｐ、ｑ、ｓが同時に０とはならない。）

(X is independently F or CF ₃ group, r is an integer of 2-6, t, u are 1 or 2, p, q are integers of 0-200, and s is an integer of 0-6, respectively. , P, q, and s are not 0 at the same time.)

（Ｘは前記と同じ、ｖ、ｗはそれぞれ１〜５０の整数である。）

(X is the same as described above, and v and w are each an integer of 1 to 50.)

（ｙは１〜１００の整数である。）

(Y is an integer of 1 to 100.)

（但し、Ｒ⁶は炭素数１〜１０のアルキル基、シクロアルキル基、アリール基、アラルキル基及びこれらの基の水素原子の一部又は全部をハロゲン原子で置換した基から選ばれる一価炭化水素基、Ｒ⁷は水素原子又はＲ⁶と同様の一価炭化水素基、Ｒ⁸は酸素原子又は炭素原子数１〜８のアルキレン基、シクロアルキレン基、アリーレン基、これらの基の水素原子の一部をハロゲン原子で置換した基、及び上記アルキレン基とアリーレン基とを組み合わせた基から選ばれる二価炭化水素基、Ｒ⁹はＲ⁶と同様の一価炭化水素基、Ｒ¹⁰はＲ⁶と同様の一価炭化水素基、又は炭素原子数２〜２０の脂肪族不飽和結合を含有する一価炭化水素基、及びこれらの基の水素原子の一部又は全部をハロゲン原子で置換した基から選ばれる一価炭化水素基を示す。） In the above formula (4), Q is a group represented by the following formula (8).

(Wherein R ⁶ is a monovalent hydrocarbon selected from alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups, aryl groups, aralkyl groups, and groups in which some or all of the hydrogen atoms in these groups have been substituted with halogen atoms. Group, R ⁷ is a hydrogen atom or a monovalent hydrocarbon group similar to R ⁶ , R ⁸ is an oxygen atom or an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group, an arylene group, one of hydrogen atoms of these groups A divalent hydrocarbon group selected from a group in which a part is substituted with a halogen atom, and a combination of the above alkylene group and arylene group, R ⁹ is a monovalent hydrocarbon group similar to R ⁶ , R ¹⁰ is R ⁶ and From the same monovalent hydrocarbon group, or a monovalent hydrocarbon group containing an aliphatic unsaturated bond having 2 to 20 carbon atoms, and a group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms Indicates the selected monovalent hydrocarbon group )

  Furthermore, in the said Formula (4), Z is a C1-C30 monovalent organic group which may have the atom chosen from oxygen, nitrogen, sulfur, and silicon in the middle of a coupling | bonding.

The reinforcing filler of the component (B) is assumed to be carbon black, fumed silica or fumed silica treated with a surface treatment agent containing silicon in the molecule.
However, since these fluorine-containing curable compositions are difficult to be blended with different types of inexpensive rubbers, the molded products are generally expensive, and their usage is limited.
Further, other rubbers may have excellent characteristics with respect to rubber physical properties and processability. Specifically, compared with silicone rubber, it is not as good as silicone rubber in terms of rubber strength, elongation, compression set, roll workability, mold releasability and the like.
Therefore, the above-mentioned fluorine-containing curable composition has the greatest characteristics of solvent resistance and chemical resistance. When the solvent and chemicals are in partial contact, only the contact portion is made into a fluorine-containing rubber molded product. For the part, a different rubber material may be preferable.

Japanese Patent No. 2990646 (Japanese Patent Laid-Open No. Hei 8-199070) JP 2000-007835 A JP 2001-106893 A JP 2003-201401 A

  The present invention has been made in view of the above circumstances, and by forming a fluorine-containing rubber composition and a different rubber composition by simultaneous crosslinking, the solvent resistance, chemical resistance, heat resistance, and low temperature characteristics of the fluorine-containing rubber are achieved. An object of the present invention is to provide a molded article having both excellent parts and characteristics of different rubbers and a method for producing the same.

As a result of intensive studies to achieve the above object, the present inventors have found that a perfluoropolyether fluororubber composition having a crosslinking site of Si—CH═CH ₂ is a different rubber composition, particularly a silicone rubber composition. As a result, it was found that simultaneous crosslinking was possible and the present invention was made.

Accordingly, the present invention provides a rubber molded article obtained by co-crosslinking the following perfluoropolyether fluororubber composition and a different rubber composition, and a method for producing the same.
Claim 1:
(A) As a crosslinking site selected from a perfluoropolyether-based fluorine-containing rubber composition whose crosslinking site is Si—CH═CH ₂ and (b) a silicone rubber composition, a fluorosilicone rubber composition, and a fluorine rubber composition A rubber molded product obtained by integrally forming a non-perfluoropolyether-based dissimilar rubber composition containing Si—CH═CH ₂ by simultaneously crosslinking and curing.
Claim 2:
The perfluoropolyether-based fluorine-containing rubber composition (a) is
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer formed by adding a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule,
(B) Crosslinkability comprising a reinforcing filler, and (C) a crosslinking agent having a hydrosilyl group in the molecule or a peroxide crosslinking agent in an amount sufficient to cure the component (A). The rubber molded article according to claim 1, which is a fluororubber composition.
Claim 3:
3. The rubber molded article according to claim 1, wherein the different rubber composition (b) is a peroxide crosslinking type silicone rubber composition or an addition crosslinking type silicone rubber composition.
Claim 4:
The different rubber composition of the above (b)
(D) Average composition formula (R ¹¹ ) _a SiO _{(4-a) / 2}
(In the formula, R ¹¹ is an unsubstituted or substituted monovalent hydrocarbon group, and a is a number satisfying 1.95 <a <2.05.)
A diorganopolysiloxane represented by the formula: 0.01 to 15 mol% of all R ¹¹ bonded to silicon atoms of the diorganopolysiloxane is a monovalent aliphatic unsaturated hydrocarbon group,
The rubber molded article according to claim 3, which is a silicone rubber composition containing (E) a reinforcing filler and (F) a crosslinking agent.
Claim 5:
The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both peroxide cross-links, and the compositions (a) and (b) are simultaneously cross-linked. The rubber molded article according to any one of claims 1 to 4, wherein the rubber molded article is obtained by integral molding .
Claim 6:
The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both addition reaction cross-linking, and the compositions (a) and (b) are simultaneously cross-linked. The rubber molded article according to any one of claims 1 to 4, wherein the rubber molded article is obtained by integral molding .
Claim 7:
(A) As a crosslinking site selected from a perfluoropolyether-based fluorine-containing rubber composition whose crosslinking site is Si—CH═CH ₂ and (b) a silicone rubber composition, a fluorosilicone rubber composition, and a fluorine rubber composition Si-CH = CH non perfluoropolyether heterogeneous rubber composition at the same time cross-cured by the production method of the rubber molded article obtained by integral molding comprising _2.
Claim 8:
The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both peroxide cross-links, and the compositions (a) and (b) are simultaneously cross-linked. The manufacturing method of Claim 7 characterized by the above-mentioned.
Claim 9:
The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both addition reaction cross-linking, and the compositions (a) and (b) are simultaneously cross-linked. the method of claim 7, wherein not characterized by Rukoto obtained by integrally molding is.
Claim 10:
A rubber product having the rubber molded product according to any one of claims 1 to 6 as a partial structure or an overall structure.
Claim 11:
The rubber product according to claim 10, which is a sealing material, an O-ring, a diaphragm, a hose, a cap or a valve material.

  ADVANTAGE OF THE INVENTION According to this invention, the molded article which has the characteristic of the different rubber | gum and the part excellent in the solvent resistance of a fluorine-containing rubber | gum, chemical resistance, heat resistance, and a low temperature characteristic can be provided.

As the perfluoropolyether-based fluorine-containing rubber composition in which the crosslinking site is Si—CH═CH ₂ used in the present invention, the above-mentioned Japanese Patent No. 2990646 (JP-A-8-199070), JP-A-2000-007835, JP-A-2001-106893, JP-A-2003-20141 and the like can be used, and the product name SIFEL series (manufactured by Shin-Etsu Chemical Co., Ltd.) is generally used. It is available.

In this case, the fluorine-containing rubber composition has two types of composition, a liquid rubber composition and a millable rubber composition. When simultaneous crosslinking is performed, the thickness of the composition can be adjusted by a roll operation. Millable rubber compositions are desirable, particularly those described in JP 2000-007835 A and JP 2001-106893 A,
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer formed by adding a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule,
(B) reinforcing filler,
(C) A crosslinkable fluororubber composition comprising a sufficient amount of a crosslinking agent or peroxide crosslinking agent having a hydrosilyl group in the molecule to cure the component (A) Things are preferred.

  On the other hand, the rubber material of the (b) different rubber composition that performs simultaneous crosslinking with the fluorine-containing rubber composition (a) requires heat treatment to stabilize the fluorine-containing rubber composition (a). Having a rubber material is desirable.

Specific examples include a silicone rubber composition and a fluororubber composition not having perfluoropolyether as a main chain, and preferably include Si—CH═CH ₂ which is a crosslinking site of the fluororubber composition. It is a silicone rubber composition.

  The silicone rubber or the silicone rubber composition here is described in detail in “Silicone Handbook” (Kunio Ito, Nikkan Kogyo Shimbun, August 31, 1990). First, mention may be made of chapter 10 liquid silicone rubber, chapter 11 modified silicone rubber, chapter 15 fluorosilicone rubber, and silicone rubber (chapter 9) and fluorosilicone rubber (chapter 15) are most preferably used.

In this case, as the silicone rubber composition in which the crosslinking site contains Si—CH═CH ₂ , peroxide crosslinking cured with an organic peroxide, a Si—H group-containing compound, and a platinum group metal catalyst are used. Addition cross-linking is generally used.

As such a silicone rubber composition, for example,
(D) The following average composition formula (I)
(R ¹¹ ) _a SiO _{(4-a) / 2} (I)
(In the formula, R ¹¹ is an unsubstituted or substituted monovalent hydrocarbon group, and a is a number satisfying 1.95 <a <2.05.)
A diorganopolysiloxane represented by the formula: 0.01 to 15 mol% of all R ¹¹ bonded to silicon atoms of the diorganopolysiloxane is a monovalent aliphatic unsaturated hydrocarbon group,
A silicone rubber composition containing (E) a reinforcing filler and (F) a crosslinking agent may be mentioned.

Here, the diorganopolysiloxane of component (D) has the following average composition formula (I)
(R ¹¹ ) _a SiO _{(4-a) / 2} (I)
(In the formula, R ¹¹ is an unsubstituted or substituted monovalent hydrocarbon group, and a is a number satisfying 1.95 <a <2.05.)
In the total R ¹¹ bonded to the silicon atom of the diorganopolysiloxane, 0.01 to 15 mol% is a monovalent aliphatic unsaturated hydrocarbon group. When the content of the aliphatic unsaturated hydrocarbon group is less than 0.01 mol%, a cured product having sufficient tear strength may not be obtained. When the content exceeds 15 mol%, the resulting cured product is obtained. May become inconvenient, and there may be inconveniences such as insufficient tear strength.

Examples of the monovalent aliphatic unsaturated hydrocarbon group include alkenyl groups having 2 to 8 carbon atoms such as a vinyl group and an allyl group. Among them, a vinyl group is preferable. In addition, as R ¹¹ other than the aliphatic unsaturated hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms can be mentioned. For example, an alkyl group such as a methyl group or an ethyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; a trifluoropropyl group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom or the like The group of these is illustrated, A preferable thing in these is a methyl group. The (D) component diorganopolysiloxane may have a hydroxyl group bonded to a silicon atom.

  In the average composition formula (I), a is a number satisfying 1.95 <a <2.05. When a is 1.95 or less, a stable linear polymer is not obtained and is easily gelled. When a is 2.05 or more, it may be difficult to become a high molecular weight polymer.

  In addition, the degree of polymerization of the (D) component diorganopolysiloxane is preferably 1,000 or more, and more preferably 2,000 or more, in order to ensure sufficient mechanical strength of the resulting cured product. It is preferable that it is preferably 3,000 to 10,000.

（式中、ｋは１以上の整数、ｍは１以上の整数であり、ｋ＋ｍは、好ましくは１，０００以上の整数であり、更に好ましくは２，０００以上の整数であり、特に好ましくは３，０００〜１０，０００の整数である。但し、ｋ及びｍは、ケイ素原子に結合する全有機基中の−ＣＨ＝ＣＨ₂基の割合が０．０１〜１５モル％となるような数値である。複数のＲ¹²は同一でも異なってもよく、メチル基、ビニル基又は水酸基である。）
で表される化合物；下記一般式（ＩＩＩ）： Specific examples of the (D) component diorganopolysiloxane include the following general formula (II):

(In the formula, k is an integer of 1 or more, m is an integer of 1 or more, k + m is preferably an integer of 1,000 or more, more preferably an integer of 2,000 or more, and particularly preferably 3). K and m are numerical values such that the proportion of —CH═CH ₂ groups in all organic groups bonded to the silicon atom is 0.01 to 15 mol%. The plurality of R ¹² may be the same or different and are a methyl group, a vinyl group or a hydroxyl group.)
A compound represented by the following general formula (III):

（式中、ｋは１以上の整数、ｍは１以上の整数、ｎは１以上の整数であり、ｋ＋ｍ＋ｎは、好ましくは１，０００以上の整数であり、更に好ましくは２，０００以上の整数であり、特に好ましくは３，０００〜１０，０００の整数である。但し、ｋ、ｍ及びｎは、ケイ素原子に結合する全有機基中の−ＣＨ＝ＣＨ₂基の割合が０．０１〜１５モル％となるような数値である。複数のＲ¹³は同一でも異なってもよく、メチル基、ビニル基、３，３，３−トリフルオロプロピル基又は水酸基である。）
で表される化合物；下記一般式（ＩＶ）：

(In the formula, k is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 1 or more, k + m + n is preferably an integer of 1,000 or more, more preferably an integer of 2,000 or more. Particularly preferably, it is an integer of 3,000 to 10,000, provided that k, m, and n have a ratio of —CH═CH ₂ groups in all organic groups bonded to silicon atoms of 0.01 to (The numerical value is 15 mol%. The plurality of R ¹³ may be the same or different and are a methyl group, a vinyl group, a 3,3,3-trifluoropropyl group or a hydroxyl group.)
A compound represented by the following general formula (IV):

（式中、ｋは１以上の整数、ｍは１以上の整数であり、ｎは１以上の整数であり、ｋ＋ｍ＋ｎは、好ましくは１，０００以上の整数であり、更に好ましくは２，０００以上の整数であり、特に好ましくは３，０００〜１０，０００の整数である。但し、ｋ、ｍ及びｎは、ケイ素原子に結合する全有機基中の−ＣＨ＝ＣＨ₂基の割合が０．０１〜１５モル％となるような数値である。複数のＲ¹⁴は同一でも異なってもよく、メチル基、ビニル基、フェニル基又は水酸基である。）
で表される化合物等が例示され、それらの中でも上記一般式（ＩＩ）で表される化合物が好ましい。

(In the formula, k is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 1 or more, k + m + n is preferably an integer of 1,000 or more, more preferably 2,000 or more. And particularly preferably an integer of 3,000 to 10,000, provided that k, m, and n have a ratio of —CH═CH ₂ groups in the total organic groups bonded to silicon atoms of 0.00. (The numerical values are from 01 to 15 mol%. The plurality of R ¹⁴ may be the same or different and are a methyl group, a vinyl group, a phenyl group, or a hydroxyl group.)
A compound represented by the general formula (II) is preferable among them.

  The (D) component diorganopolysiloxane can be produced by a known method, for example, a cyclic polysiloxane (siloxane) obtained by (co) hydrolyzing one or more organohalosilanes. In the presence of a basic catalyst or an acidic catalyst.

The reinforcing filler of component (E) imparts mechanical strength to the resulting cured product. For example, fumed silica, precipitated silica, fused silica, quartz powder, diatomaceous earth, aluminum silicate, oxidation Examples thereof include titanium, zinc oxide, iron oxide, alumina, calcium carbonate, zinc carbonate, and carbon black. Among them, it is preferable to use silica in order to make the reinforcing property sufficient, and usually a specific surface area of 10 m ² / g or more, preferably 100 m ² / g or more is used. Particularly preferably, fumed silica and precipitated silica having a specific surface area of 100 to 400 m ² / g are used. In addition, the reinforcing filler of component (E) not only provides mechanical strength to the resulting cured product, but also imparts electrical conductivity, thermal conductivity, and the like.

Examples of the reinforcing filler of the component (E) include chlorosilanes such as (CH ₃ ) ₃ SiCl, (CH ₃ ) ₂ SiCl ₂ , (CH ₃ ) SiCl ₃ ; CH ₂ ═CHSi (OCH ₃ ) ₃ , ( Alkoxysilanes such as CH ₃ ) ₂ Si (OCH ₃ ) ₂ and CH ₃ Si (OCH ₃ ) ₃ ; organosilazanes such as (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ ;

（式中、ｉ及びｊは、ｉ＞０、ｊ＞１、１＜ｉ＋ｊ＜１００を満たす数である。）
で表されるシリコーンオイル等の表面処理剤で表面処理したものも使用可能である。また、表面処理剤の加水分解性を調整、促進するために少量の水を添加してもよい。

(Where i and j are numbers satisfying i> 0, j> 1, 1 <i + j <100).
Those treated with a surface treatment agent such as silicone oil can be used. A small amount of water may be added to adjust and promote the hydrolyzability of the surface treatment agent.

  (E) The compounding quantity of a component is the range of 5-200 mass parts normally with respect to 100 mass parts of (D) component, Preferably it is the range of 10-100 mass parts. When the blending amount of the component (E) is too small, the processability is insufficient and a sufficient reinforcing effect cannot be obtained, and when it is too large, the workability, mold flowability at the time of processing, etc. are reduced, or the silicone rubber machine In some cases, the target strength may decrease.

  (F) The crosslinking agent of a component should just be a thing which can harden the silicone rubber composition of this invention. As the component (F), a combination of an organohydrogenpolysiloxane and a platinum group metal catalyst or an organic peroxide can be used depending on the curing method.

  As the component (F), an organohydropolypolysiloxane in the case of using a combination of an organohydrogenpolysiloxane and a platinum group metal catalyst is one having at least two Si-H groups in one molecule. The structure used may be any of linear, cyclic or branched structures. The Si—H group may be at the end of the molecular chain or in the middle of the molecular chain. Furthermore, it is usually preferable to use an organohydrogenpolysiloxane having a polymerization degree of 300 or less.

Specifically, the organohydrogenpolysiloxane includes a diorganopolysiloxane terminated with a dimethylhydrogensilyl group; a copolymer comprising dimethylsiloxy units, methylhydrogensiloxy units, and terminal trimethylsiloxy units; Low viscosity fluid comprising dimethylhydrogensiloxy units and SiO ₂ units; 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane; 1-propyl-3,5 , 7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane; 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane Illustrated. In the organohydrogenpolysiloxane, the Si-H group contained in the organohydrogenpolysiloxane is usually 0.5 to 3.0 mol, preferably 1 per mol of the aliphatic unsaturated hydrocarbon group of the diorganopolysiloxane (D) component. It is preferable to use an amount of 0.0 to 2.0 mol.

  The platinum group metal catalyst is used as a catalyst for the hydrosilylation reaction between the aliphatic unsaturated hydrocarbon group of the (D) component diorganopolysiloxane and the Si-H group in the organohydrogenpolysiloxane. And is usually in the range of 0.1 to 2,000 ppm, preferably 1 to 1,000 ppm (as a platinum group metal) with respect to the total amount of the organopolysiloxane of component (D) and the organohydrogenpolysiloxane. Used in. Examples of such platinum group metal-based catalysts include finely divided metal platinum catalysts described in US Pat. No. 2,970,150, and chlorides described in US Pat. No. 2,823,218. Platinum acid catalysts, platinum-hydrocarbon complex compounds described in US Pat. No. 3,159,601 and US Pat. No. 3,159,662, US Pat. No. 3,516,946 Platinum-based chloroplatinic acid-olefin complex compounds described in US Pat. No. 3,775,452 and platinum-vinylsiloxane complexes described in US Pat. No. 3,814,780 A catalyst or the like can be used.

  When the combination of organohydrogenpolysiloxane and platinum group metal catalyst is used as component (F) and the silicone rubber composition of the present invention is cured by hydrosilylation reaction, the storage stability at room temperature is good. In order to maintain an appropriate pot life, it is also possible to add a reaction control agent such as acetylene alcohols such as methylvinylcyclotetrasiloxane and ethynylcyclohexanol. Curing by the hydrosilylation reaction is performed by heating at a temperature of 60 to 400 ° C. for about 1 minute to 5 hours.

  When an organic peroxide is used as the component (F), the organic peroxide is usually 0.01 to 3 parts by mass, preferably 0.05 to 100 parts by mass of the (D) component diorganopolysiloxane. -1 mass part is mix | blended. As the organic peroxide, those usually used for curing organic peroxide-curing silicone rubber can be used without any particular restriction. Specifically, for example, benzoyl peroxide, bis ( 2,4-dichlorobenzoyl) peroxide, di-t-butyl peroxide, 2,5-dimethyl-di-t-butylperoxyhexane, t-butylperbenzoate, t-butylperoxyisopropyl carbonate, dicumylper Examples include oxides. These may be used alone or in combination of two or more.

  When the organic peroxide is used as the component (F) and the composition of the present invention is cured, the composition is usually heated at a temperature of 100 to 400 ° C. for about 1 minute to 5 hours.

  Moreover, as (F) component, the combination of said organohydrogen polysiloxane and a platinum group metal catalyst and an organic peroxide can also be used together.

  In addition, the fluorine-containing rubber composition used in the present invention can be peroxide-crosslinked and addition-crosslinked similarly to the silicone rubber composition.

  As a combination of cross-linking forms for simultaneous cross-linking, the same cross-linking system (for example, a peroxide cross-linked silicone composition and a peroxide cross-linked fluorine-containing rubber composition) is used for the fluorine-containing rubber composition and the silicone rubber composition. The interface is also stable, but simultaneous molding is possible even if the crosslinking system is different.

  In addition to the silicone rubber composition, any material that can be cross-linked at the same time can be a composition of any material that can be cross-linked with peroxide. However, considering heat resistance, this type of fluoro rubber does not have perfluoropolyether as the main chain. A composition.

  In the fluororubber composition not having perfluoropolyether as the main chain, the base polymer is a highly fluorinated elastic copolymer, which is an elastic copolymer of vinylidene fluoride and hexafluoropropene, pentafluoropropene. , Trifluoroethylene, vinyl fluoride, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), etc., or an elastic polymer or an elastic copolymer with two or more types are exemplified. Then, vinylidene fluoride-hexafluoropropene binary elastic copolymer and vinylidene fluoride-tetrafluoroethylene-hexafluoropropene ternary elastic copolymer are preferable. In this case, the base polymer can be crosslinked using the organic peroxide described above. In addition, the addition amount of an organic peroxide is 0.01-3 mass parts with respect to 100 mass parts of base polymers, Especially 0.05-1 mass part.

Next, a method for manufacturing a simultaneous molded product will be described with reference to the drawings.
In order to process a molded product such as a rubber cap (medicinal plug) shown in FIG. 1, the fluorine-containing rubber composition 2 is placed in a mold where chemical resistance is required, and the chemical resistance is insoluble. May be press-molded with a different rubber composition 1, for example, a silicone rubber composition.

  FIG. 2 shows a case where a two-layer rubber sheet is formed. The fluorine-containing rubber composition 2 and the different rubber composition 1 whose thickness is adjusted by a two-roll rubber roll or a calender roll are bonded together and pressed with a mold. Alternatively, it can be easily produced by HAV crosslinking.

  FIG. 3 shows a three-layer structure produced by the same manufacturing method as in FIG. 2. The chemical resistance of the fluorine-containing rubber composition 2 is obtained at the surface portion, and compression set and rubber strength characteristics are sandwiched between two layers. The improved different rubber material 1 can be improved.

  The curing condition of the molded article of the present invention is preferably 1 to 30 minutes at 100 to 200 ° C. as a primary cure in both peroxide crosslinking and addition crosslinking. If it is less than 100 ° C., the curing time becomes long, so that the industrial productivity may be inferior. If it exceeds 200 ° C., there is a risk of scorch generation, so 100 to 200 ° C. is preferable, and further 120 to 170 ° C. Is preferred. The curing time in that case may be appropriately selected as the time for completing the crosslinking reaction. Moreover, in order to stabilize the physical property of this composition, it is preferable to carry out secondary cure by heat processing for about 1 to 24 hours at 100-230 degreeC. The secondary cure is less effective at less than 100 ° C and may be thermally decomposed at more than 230 ° C. More preferably, it is suitable at 150 to 200 ° C. for 1 to 20 hours.

  The molded article of the present invention can be used for various applications. In other words, rubber parts for automobiles that require oil resistance, specifically diaphragms for fuel regulators, diaphragms for pulsation dampers, diaphragms for oil pressure switches, diaphragms for EGR, canister valves, power control, etc. Rubber parts for chemical plants, such as valves such as valves, O-rings such as O-rings for quick connectors and O-rings for injectors, or sealing materials such as oil seals and cylinder head gaskets, specifically Diaphragms for pumps, valves, O-rings, hoses, packings, oil seals, rubber parts for ink jet printers, rubber parts for semiconductor production lines, and more specifically equipment that comes into contact with chemicals Die for Rubber parts for analysis and physics and chemistry equipment, such as valves that require low friction and wear resistance, such as seals such as flamm, valves, O-rings, packings, gaskets, etc. Specifically, diaphragms for valves, valves, seal parts (O-rings, packing, etc.), rubber parts for medical equipment, specifically pumps, valves, joints, etc., tent film materials, sealants, molded parts, extruded parts, coating materials, copier roll materials, electrical It is useful for moisture-proof coating materials, potting materials for sensors, sealing materials for fuel cells, laminated rubber cloths, etc.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Composition A used in Examples and Comparative Examples : Perfluoropolyether-based fluorine-containing rubber composition (I): SIFEL5701 (manufactured by Shin-Etsu Chemical Co., Ltd., containing components (A) to (C), addition cross-linkable / millable Type standard composition)
B: Perfluoropolyether-based fluorine-containing rubber composition (II): SIFEL 9700 (manufactured by Shin-Etsu Chemical Co., Ltd., containing components (A) to (C), peroxide crosslinking / millable type standard compounding composition)
C: Silicone rubber composition (I): KE951 peroxide cross-linking, containing (D) to (F) components, standard blending composition (manufactured by Shin-Etsu Chemical Co., Ltd.)
D: Silicone rubber composition (II): KE951 addition crosslinking, containing (D) to (F) components, standard blending composition (manufactured by Shin-Etsu Chemical Co., Ltd.)
E: Fluorosilicone rubber composition: FE471 (manufactured by Shin-Etsu Chemical Co., Ltd., peroxide crosslinking, standard blend composition)
F: Vinylidene-based fluororubber composition: Viton GLT (manufactured by DuPont, peroxide cross-linked, standard composition)

Manufacture of molded article for evaluation In order to obtain a molded article having the structure shown in FIG.
(1) The rubber composition is divided into 1.1 to 1.3 mm sheets with two rolls for rubber.
(2) The separated rubber composition is laminated while paying attention to air mixing.
(3) Cut the laminated sheet into 10 cm squares to prepare a preform sheet.
(4) The obtained preform sheet is charged into a 10 cm square 2 mm thick mold.
(5) After crosslinking at 170 ° C. for 10 minutes with a 75-ton press for rubber, post-curing is performed at 200 ° C. for 4 hours.

[Interfacial adhesion (simultaneous crosslinking) evaluation method]
(1) Peeled state: The degree of rubber peeling at the interface when the slit was cut with a cutter knife near the rubber interface and peeled was evaluated.
○: Rubber cohesive failure and material interface is stable △: Peeling at rubber material interface but partial cohesive failure occurs x: Peeling without cohesive failure at interface (2) Solvent swelling: Toluene (vs. Silicone) or methyl ethyl ketone (vs. fluorosilicone, vinylidene-based fluororubber) was immersed for 24 hours to evaluate the state when only one rubber material was swollen.
○: Stable rubber interface state that does not peel even when one rubber swells ×: Peels within 24 hours

[Examples 1-7]
Evaluations were made on molded articles obtained by simultaneously crosslinking different types of rubber materials in the combinations shown in Table 1. In both cases, the simultaneous cross-linking interface was stable, and it was possible to produce an integrally molded product of a fluorine-containing rubber and a different rubber material.

[Comparative Example 1]
Table 2 shows the results of evaluating silicone rubber and fluororubber as different rubber materials in the same manner as in the examples. Even the same peroxide-crosslinked rubber material could not be cross-linked simultaneously, and easily peeled off at the interface.

It is sectional drawing which shows an example of the rubber molded product of this invention. It is sectional drawing which shows the other example of the rubber molded product of this invention. It is sectional drawing which shows another example of the rubber molded product of this invention.

Explanation of symbols

1 Different rubber material 2 Perfluoropolyether fluoro rubber

Claims (11)

(A) As a crosslinking site selected from a perfluoropolyether-based fluorine-containing rubber composition whose crosslinking site is Si—CH═CH ₂ and (b) a silicone rubber composition, a fluorosilicone rubber composition, and a fluorine rubber composition A rubber molded product obtained by integrally forming a non-perfluoropolyether-based dissimilar rubber composition containing Si—CH═CH ₂ by simultaneously crosslinking and curing. The perfluoropolyether-based fluorine-containing rubber composition (a) is
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer formed by adding a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule,
(B) Crosslinkability comprising a reinforcing filler, and (C) a crosslinking agent having a hydrosilyl group in the molecule or a peroxide crosslinking agent in an amount sufficient to cure the component (A). The rubber molded article according to claim 1, which is a fluororubber composition.   3. The rubber molded article according to claim 1, wherein the different rubber composition (b) is a peroxide crosslinking type silicone rubber composition or an addition crosslinking type silicone rubber composition. The different rubber composition of the above (b)
(D) Average composition formula (R ¹¹ ) _a SiO _{(4-a) / 2}
(In the formula, R ¹¹ is an unsubstituted or substituted monovalent hydrocarbon group, and a is a number satisfying 1.95 <a <2.05.)
A diorganopolysiloxane represented by the formula: 0.01 to 15 mol% of all R ¹¹ bonded to silicon atoms of the diorganopolysiloxane is a monovalent aliphatic unsaturated hydrocarbon group,
The rubber molded article according to claim 3, which is a silicone rubber composition containing (E) a reinforcing filler and (F) a crosslinking agent. The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both peroxide cross-links, and the compositions (a) and (b) are simultaneously cross-linked. The rubber molded article according to any one of claims 1 to 4, wherein the rubber molded article is obtained by integral molding . The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both addition reaction cross-linking, and the compositions (a) and (b) are simultaneously cross-linked. The rubber molded article according to any one of claims 1 to 4, wherein the rubber molded article is obtained by integral molding . (A) As a crosslinking site selected from a perfluoropolyether-based fluorine-containing rubber composition whose crosslinking site is Si—CH═CH ₂ and (b) a silicone rubber composition, a fluorosilicone rubber composition, and a fluorine rubber composition Si-CH = CH non perfluoropolyether heterogeneous rubber composition at the same time cross-cured by the production method of the rubber molded article obtained by integral molding comprising _2.   The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both peroxide cross-links, and the compositions (a) and (b) are simultaneously cross-linked. The manufacturing method of Claim 7 characterized by the above-mentioned. The cross-linking systems of the perfluoropolyether-based fluorine-containing rubber composition (a) and the different rubber composition (b) are both addition reaction cross-linking, and the compositions (a) and (b) are simultaneously cross-linked. the method of claim 7, wherein not characterized by Rukoto obtained by integrally molding is.   A rubber product having the rubber molded product according to any one of claims 1 to 6 as a partial structure or an overall structure.   The rubber product according to claim 10, which is a sealing material, an O-ring, a diaphragm, a hose, a cap or a valve material.

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