JP2003183466A - Fluororubber composition and its molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a peroxide-crosslinkable fluororubber composition excellent in mold release properties on crosslinking molding and a molded article obtained by molding and crosslinking the composition. <P>SOLUTION: The peroxide-crosslinkable fluororubber composition comprises a fluororubber (A) not containing a polymerized unit of vinylidene fluoride, an organic peroxide (B), and an amine compound (C) and/or an organic onium compound (D), where the mass ratio of the fluororubber (A): the organic peroxide (B): the amine compound (C) and/or the organic onium compound (D) is 100:(0.3-10):(0.01-5). The molded article is obtained by molding and crosslinking the composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a peroxide-crosslinkable fluororubber composition and a molded article thereof, and more specifically to a peroxide-crosslinkable fluororubber composition excellent in mold releasability at the time of crosslinking molding and a composition thereof. The present invention relates to a molded product obtained by molding and crosslinking a product.

[0002]

2. Description of the Related Art In recent years, the environment around the engine has become higher due to the higher output of automobile engines and the compactness of the engine room. In addition, a highly basic amine-based additive is added to the currently used high-performance engine oil in order to improve heat resistance. for that reason,
A rubber-based sealing material is required to have characteristics suitable for such an environment. Generally, fluororubber is known as a rubber material having excellent heat resistance and oil resistance, but fluororubber containing a polymerized unit of vinylidene fluoride is dehydrofluorinated by a highly basic amine-based additive at high temperature. May occur and deteriorate easily, and it may not have sufficient durability against recent high performance engine oils. On the other hand, a fluororubber containing no polymerized units of vinylidene fluoride is less likely to undergo a dehydrofluorination reaction due to an amine-based additive, and is also excellent in engine oil resistance and its durability. However, when the fluororubber containing no polymerized units of vinylidene fluoride is peroxide-crosslinked, the mold releasability may not be sufficient during crosslink molding.

In molding fluororubber with a compression molding machine, an appropriate mold release agent is used to improve the mold releasability of the fluororubber molded product. A release agent such as a silicone emulsion-based release agent or a fluorine-based release agent is used. But,
These mold release agents, which are called external mold release agents, need to be applied to the mold for each molding, and also cause mold stains. As a means for solving this problem, a method of incorporating a release agent (hereinafter referred to as an internal addition type release agent) into the fluororubber composition has been studied.

JP-A-2-281062 discloses a mixture of a peroxide crosslinkable fluororubber composition with an aliphatic carboxylic acid metal salt as an internal addition type release agent, and an aliphatic bisamide or an N-substituted fatty acid amide. A method of blending is disclosed. However, the fluororubber composition containing these internal addition type release agents has a problem that the mold releasability is not sufficient and the characteristics of the molded product are not sufficient.

Japanese Unexamined Patent Publication (Kokai) No. 11-124482 discloses a method of improving the mold releasability of a peroxide-crosslinkable fluororubber composition by blending an ethylene-propylene copolymer. However, when the number of moldings increases, the mold releasability deteriorates, and the engine oil resistance of the molded product was not sufficient. Therefore, the conventional mold release agents have problems such as causing mold stains, insufficient mold releasability, and deterioration of physical properties of molded articles.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a peroxide crosslinkable fluororubber composition having excellent mold releasability during crosslink molding, and a molded article obtained by molding and crosslinking the composition. Is to provide.

[0007]

The present invention is directed to a fluororubber (A) containing no polymerized units of vinylidene fluoride, an organic peroxide (B), and an amine compound (C) and / or an organic onium compound ( A fluororubber composition containing D), wherein the mass ratio of fluororubber (A): organic peroxide (B): amine compound (C) and / or organic onium compound (D) is 100: 0.3. A peroxide crosslinkable fluororubber composition, characterized in that it is 10: 0.01 to 5 is provided.

The present invention also provides a molded article obtained by molding and crosslinking the above-mentioned peroxide-crosslinkable fluororubber composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Fluorine rubber (A) according to the present invention
Is a fluororubber containing no polymerized units of vinylidene fluoride. As a specific example, a tetrafluoroethylene (hereinafter referred to as TFE) / propylene (hereinafter referred to as P) copolymer, hexafluoropropylene (hereinafter referred to as H)
FP. ) / Ethylene (hereinafter referred to as E) copolymer, TFE / perfluoro (alkyl vinyl ether) (hereinafter referred to as PFAV) copolymer, PFAV /
E copolymer, fluorosilicone, fluorophosphazene and the like can be mentioned. Preferred are TFE / P copolymers, TFE / PFAV copolymers and HFP / E copolymers. It is also preferable that the polymer chain of fluororubber has a functional group such as a double bond.

The molar ratio of TFE polymerized units / P polymerized units in the TFE / P copolymer is 40/60 to 70/3.
0 is preferable, and 50/50 to 60/40 is more preferable. In addition, in the TFE / PFAV copolymer, PFA
The perfluoroalkyl group of V preferably has 1 to 8 carbon atoms, and the perfluoroalkyl group may contain an etheric oxygen atom. Examples of the perfluoroalkyl group include a CF ₃ group, a C ₃ F ₇ group, a C ₃ F ₇ OC ₃ F ₆ group, and a C group.
_{A 3} F ₇ OC ₃ F ₆ OC ₃ F ₆ group is more preferred. Also,
Polymerization unit of TFE in TFE / PFAV copolymer /
The molar ratio of the polymerized units of PAVE is 85/15 to 25/7.
5 is preferable, and 75/25 to 50/50 is more preferable. Polymerized unit of HFP / E in HFP / E copolymer
15 / 85-75 / 25 are preferable and, as for the molar ratio of the polymerization unit of, 40 / 60-60 / 40 are more preferable.

The organic peroxide (B) in the present invention is a cross-linking agent and is preferably one which generates a peroxide radical by heating or the like. Specific examples include ditert-butyl peroxide, tert-butylcumyl peroxide,
Dicumyl peroxide, α, α-bis (tert-butylperoxy) -p-diisopropylbenzene, 2,5
-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert
-Butylperoxy) hexane-3 and other dialkyl peroxides, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-
Dimethylhexane-2,5-dihydroxyperoxide, benzoyl peroxide, tert-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxymaleic acid, tert-butylperoxysopropylcarbonate Etc. Particularly preferred are dialkyl peroxides. Generally, the type of the organic peroxide to be used and the content in the fluororubber composition are selected from the activity of the organic peroxide, the decomposition temperature and the like.

The content of the organic peroxide (B) is 0.3 to 10 parts by mass with respect to 100 parts by mass of fluororubber.
Within this range, crosslinked physical properties with a good balance of strength and elongation can be obtained. It is preferably 0.3 to 5 parts by mass,
It is more preferably 0.5 to 3 parts by mass.

By containing the amine compound (C) and / or the organic onium compound (D) in the fluororubber composition of the present invention, the mold releasability of the fluororubber composition during molding is improved.

The content of the amine compound (C) and / or the organic onium compound (D) is 0.01 to 5 parts by mass in total with respect to 100 parts by mass of the fluororubber. When the content of the amine compound (C) and / or the organic onium compound (D) is within this range, the mold releasing property is particularly excellent, molding defects do not occur, and the physical properties of the molded product do not deteriorate. ,preferable. The content is preferably 0.1 to 2 parts by mass.

Specific examples of the amine compound (C) include:
1,8-diazabicyclo [5.4.0] undec-7-
Ene, 1,5-diazabicyclo [4.3.0] nona-5
-Ene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] undeca-7-ene and other diazabicyclo compounds, triethylamine, tributylamine, stearylamine, etc. One basic nitrogen is bonded to the molecule. Amine compounds, 1,6-hexamethylenediamine, ethylenediamine, etc. Amine compounds that bind two or more basic nitrogens in the molecule, N, N'-dicinnamylidene-1,6-hexamethylenediamine, etc., Schiff bases, ethylenediamine carbamate , Hexamethylene diamine carbamate, 4,4′-diamine cyclohexyl methane carbamate and the like.

Particularly, an amine compound or one of the above diazabicyclo compounds having one basic nitrogen atom bonded in the molecule is preferable, a diazabicyclo compound is more preferable, and 1,8
-Diazabicyclo [5.4.0] undec-7-ene is most preferred.

As the organic onium compound (D), organic quaternary ammonium hydroxide (d1), organic quaternary ammonium hydrogensulfate (d2), organic phosphonium salt,
Organic quaternary ammonium salts and the like are preferred. More preferably, R ¹ R ² R ³ R ⁴ NOH (wherein R ¹ , R ² , R
³ and R ⁴ are the same or different and have 1 to 20 carbon atoms.
Valent hydrocarbon radical. ) Organic quaternary ammonium hydroxide (d1) and R ⁵ R ⁶ R ⁷ R ⁸ NHSO ₄
(Here, R ⁵ , R ⁶ , R ⁷ or R ⁸ are the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms.) From organic quaternary ammonium hydrogensulfate (d2) It is at least one organic onium salt selected from the group consisting of:

R ¹ , R ² , R ³ and R ⁴ are preferably monovalent hydrocarbon groups having 1 to 8 carbon atoms. In addition, R ⁵ , R
⁶ , R ⁷ or R ⁸ is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms. With this number of carbon atoms, the mold releasability of the molded product of the fluororubber composition is further improved.

Organic quaternary ammonium hydroxide (d
Specific examples of 1) include tetrabutylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trioctylmethylammonium hydroxide, tridodecylmethylammonium hydroxide and trimethylbenzylammonium hydroxide.

Organic quaternary ammonium hydrogensulfate (d2)
Specific examples thereof include organic quaternary ammonium hydrogensulfate such as tetrabutylammonium hydrogensulfate, tetraethylammonium hydrogensulfate, trioctylmethylammonium hydrogensulfate and trimethylbenzylammonium hydrogensulfate.

Specific examples of the organic phosphonium salt include tetrabutylphosphonium chloride, triphenylbenzylphosphonium chloride, tributyl (methoxypropyl) phosphonium chloride, diethylaminobenzyldiphenylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylphosphonium bromide. , Tetrabutylphosphonium bromide, tetrabutylphosphonium benzotriazolate, and the like.

Specific examples of the organic quaternary ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide and 1,8-diazabicyclo [5.4.0] undecene-7. Examples thereof include p-toluenesulfonate.

In particular, organic quaternary ammonium hydroxide and organic quaternary ammonium hydrogensulfate are preferable, and tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide and tetrabutylammonium hydrogensulfate are more preferable.

The amine compound (C) and / or the organic onium compound (D) may be used alone or in combination of two or more kinds.

The fluororubber composition of the present invention preferably contains a crosslinking aid. When the crosslinking aid is contained, the generated radicals effectively react with the crosslinking agent to increase the crosslinking efficiency. Examples of the cross-linking aid include compounds having reactivity with peroxide radicals and radicals on the molecule of fluororubber.

Specific examples include triallyl cyanurate, triallyl isocyanurate, trimetallyl isocyanurate, triacrylic formal, triallyl trimellitate, N, N'-m-phenylene bismaleimide, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, dipropargyl terephthalate, diallyl phthalate, N, N ', N ", N"'-tetraallyl terephthalamide, polymethyl vinyl siloxane, polymethyl phenyl vinyl siloxane, etc. Examples thereof include vinyl group-containing siloxane oligomers.

Particularly, triallyl cyanurate, triallyl isocyanurate and trimetallyl isocyanurate are preferable, and triallyl isocyanurate is more preferable.

The content of the crosslinking aid is preferably 0.1 to 10 parts by mass, and 0.5 to 100 parts by mass with respect to 100 parts by mass of the fluororubber.
5 parts by mass is more preferable. Within this range, crosslinked physical properties with a good balance of strength and elongation can be obtained.

In the present invention, it is also preferable to use a polymer that can be crosslinked with an organic peroxide in addition to the fluororubber. By using a polymer that can be crosslinked by an organic peroxide together with a co-crosslinking agent, it is possible to improve the flexibility at low temperature and reduce the specific gravity.

Polymers that can be cross-linked with an organic peroxide include silicone rubber, ethylene / vinyl acetate copolymer, poly-1,2-butadiene, ethylene / propylene /
Diene copolymer, epichlorohydrin rubber, polyurethane rubber, halogenated butyl rubber, acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber,
Vinyl group-containing acrylic rubber and the like can be mentioned. The content of the polymer that can be crosslinked by the organic peroxide is 1
0.1 to 50 parts by mass is preferable with respect to 00 parts by mass, and 1
-20 parts by mass is more preferred.

In addition to the above, various compounding agents which are compounded with usual rubber can be added to the fluororubber composition of the present invention. Specific examples include metal oxides such as magnesium oxide, calcium oxide, titanium oxide, silicon oxide, zinc oxide, lead oxide and aluminum oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, zinc hydroxide, lead hydroxide. Etc., metal hydroxides, magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate, etc., carbonates, magnesium silicate, calcium silicate, sodium silicate, aluminum silicate, etc. silicates, aluminum sulfate, calcium sulfate, barium sulfate, etc. sulfuric acid Salt, metal sulfide such as molybdenum disulfide, iron sulfide, copper sulfide, diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfate mixture), graphite, carbon black, fluorocarbon, calcium fluoride, coke, wollastonite, Mica powder, glass powder, carbon fiber, etc. It is below. These compounding agents may be used alone or in combination of two or more.

The content of the compounding agent is 100% fluororubber.
0.1 to 60 parts by mass is preferable with respect to parts by mass, and 0.
It is more preferably 1 to 40 parts by mass. In addition, a colorant, a flame retardant, a stabilizer, a plasticizer, an oil resistance improver, a scorch inhibitor, etc. may be added.

In the fluororubber composition of the present invention, it is also preferable to further add a conventionally known processing aid.
Specific examples include natural waxes such as carnauba wax and shellac wax, higher fatty acids such as stearic acid, oleic acid and palmitic acid, saturated or unsaturated sodium stearate, zinc stearate, potassium laurate, sodium oleate and the like. The fatty acid metal salts, low molecular weight polyethylene, petrolatum, aliphatic hydrocarbons such as paraffin, higher fatty acid esters such as ethyl oleate, silicone oils, diphenyl sulfone and the like.

As the method for producing the fluororubber composition of the present invention, it is preferable to mix the fluororubber with the above-mentioned various compounding ingredients by using a kneading machine such as an ordinary open roll, kneader or Banbury mixer. . Further, it is preferable that the fluororubber composition of the present invention is crosslinked under ordinary fluororubber crosslinking conditions. For example, a fluororubber composition,
It is preferable to perform press-crosslinking by placing in a mold and holding at 150 to 200 ° C. and a pressure of 0.3 to 15 MPa for 1 to 60 minutes. In this way, the fluororubber composition is molded and crosslinked. It is also preferable that the molded product taken out of the mold is held in an oven at 180 to 260 ° C. for 0.5 to 24 hours to carry out secondary crosslinking.

The molded article of the present invention is useful as an O-ring, packing, automobile parts, general industrial parts and the like.

[0036]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. Examples 1 to 3 and Examples 10 to 12 are examples, and Examples 4 to 9 and Examples 13 to
16 is a comparative example.

[Mold release rate] Using a mold with a hard chrome plating finish, press-crosslinking was continuously performed 5 times at a press pressure of 13 MPa and a press temperature of 180 ° C. for 10 minutes, and P
A -38 type O-ring was molded. The mold used was one capable of molding nine O-rings at a time. Molding was carried out 5 times, and the number of O-rings released from the mold when trying to manually peel off 9 O-rings together with burrs from the mold together with the total number of moldings ( The mold releasability was evaluated by expressing it as a percentage (hereinafter referred to as the mold release rate) with respect to 45 pieces. It is indicated that the larger the mold release rate is, the more excellent the mold releasability is.

[Example 1] 10 of tetrafluoroethylene / propylene copolymer (Aflas 150P, manufactured by Asahi Glass Co., Ltd.)
0 g, carbon black N-990 (manufactured by Cancarb)
25 g, 5 g of triallyl isocyanurate, α,
1 g of α′-bis (tert-butylperoxy) -p-diisopropylbenzene, 1 g of carnauba wax and 1,8-diazabicyclo [5.4.0] undec-7
-0.2 g of ene 1 at room temperature using an open roll
The mixture was kneaded for 5 minutes to obtain a fluororubber composition.

Then, the mold release property of the obtained fluororubber composition during cross-linking molding was evaluated. In addition, JIS K63
According to No. 01, tensile strength, elongation and hardness of the molded product were measured. In addition, the oil resistance of the molded product was measured. The oil resistance test was carried out using Toyota SJ class engine oil as the immersion oil under the conditions of 175 ° C. for 168 hours, and the tensile strength, elongation at break, hardness and volume of the molded product after the test were measured. Then, the rate of change in tensile strength, elongation at break and volume and change in hardness before and after the oil resistance test were calculated. The results are shown in Table 1.

Example 2 1,8-diazabicyclo [5.
4.0] Undeka-7-ene was replaced with 0.2 g of tetrabutylammonium hydrogensulfate in the same manner as in Example 1 except that 0.5 g of tetrabutylammonium hydrogensulfate was used to mold the O-ring to improve mold releasability. evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 1.

Example 3 1,8-diazabicyclo [5.
4.0] Undeca-7-ene was replaced with 0.2 g of tetrabutylammonium hydroxide in an amount of 1 g of a 40% methanol solution, and an O-ring was molded in the same manner as in Example 1 except for releasing the mold. The moldability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 1.

Example 4 (Comparative Example) The same as Example 1 except that 1 g of stearic acid amide was used instead of 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene. Then, an O-ring was molded and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 1.

Example 5 (Comparative Example) The same as Example 1 except that 1 g of stearic acid was used instead of 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene. , Mold releasability, normal physical properties and oil resistance were measured. The results are shown in Table 1.

Example 6 (Comparative Example) The same as Example 1 except that 1 g of zinc stearate was used instead of 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene. Then, an O-ring was molded and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 1.

[Example 7 (Comparative Example)] An O-ring was molded in the same manner as in Example 1 except that 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene was not used. The mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 1.

Example 8 (Comparative Example) 100 g of a tetrafluoroethylene / propylene / vinylidene fluoride copolymer (Aflas 200, manufactured by Asahi Glass Co., Ltd.) was used instead of 100 g of the tetrafluoroethylene / propylene copolymer. In the same manner as in Example 1, an O-ring was molded and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 1. Afras 20
In the oil resistance test, the molded product obtained from the composition using No. 0 exhibited a large change rate of strength and elongation as compared with Afras 150P.

[Example 9 (Comparative Example)] Instead of 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene, an ethylene-propylene rubber (manufactured by JSR Corporation, EP
O-in the same manner as in Example 1 except that 5 g of -21) was used.
The ring was molded and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 1.
Shown in.

The symbols in Table 1 represent the following compounds. A: tetrafluoroethylene / propylene copolymer (Aflas 150P manufactured by Asahi Glass Co., Ltd.), B: tetrafluoroethylene / propylene / vinylidene fluoride copolymer (Aflas 200 manufactured by Asahi Glass Co., Ltd.), C: carbon black N-99
0, D: triallyl isocyanurate, E: α, α′-
Bis (tert-butylperoxy) -p-diisopropylbenzene, F: carnauba wax, G: 1,8-diazabicyclo [5.4.0] undec-7-ene, H:
Tetrabutylammonium hydrogen sulfate, I: 40% methanol solution of tetrabutylammonium hydroxide,
J: stearic acid amide, K: stearic acid, L: zinc stearate, M: ethylene-propylene rubber (JS
R-21, EP-21).

[0049]

[Table 1]

Example 10 100 g of a tetrafluoroethylene / perfluoro (propyl vinyl ether) / ethylene / 1,4-hexadiene copolymer (copolymerization composition 61/31/6/2 mol%) produced by emulsion polymerization,
25 of carbon black N-990 (made by Cancarb)
g, 4 g of trimethallyl isocyanurate, 2 g of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1 g of carnauba wax, 1 g of calcium hydroxide, and 1,8-diazabicyclo [5. 4.
[0] 0.2 g of undeca-7-ene was mixed and roll kneaded at room temperature for 20 minutes using an open roll to obtain a fluororubber composition.

Then, an O-ring was molded from the obtained fluororubber composition in the same manner as in Example 1 and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 2.

Example 11 1,8-diazabicyclo [5.
4.0] Undeca-7-ene was replaced with 0.2 g of tetrabutylammonium hydrogensulfate in the same manner as in Example 10 except that 0.5 g of tetrabutylammonium hydrogensulfate was used to mold the O-ring to improve mold releasability. evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 2.

[Example 12] 1,8-diazabicyclo [5.
4.0] Undeca-7-ene was replaced with 0.2 g of tetrabutylammonium hydroxide in an amount of 1 g of a 40% methanol solution, and an O-ring was molded in the same manner as in Example 9 except for releasing the mold. The moldability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 2.

[Example 13 (Comparative Example)] Example 1 except that 1 g of stearic acid amide was used instead of 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene.
An O-ring was molded in the same manner as in 0, and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 2.

Example 14 (Comparative Example) Example 10 was repeated except that 1 g of stearic acid was used instead of 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene. , O-rings were molded and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 2.

Example 15 (Comparative Example) Example 10 except that 1 g of zinc stearate was used instead of 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene.
The O-ring was molded in the same manner as described above, and the mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 2.

[Example 16 (Comparative Example)] An O-ring was molded in the same manner as in Example 10 except that 0.2 g of 1,8-diazabicyclo [5.4.0] undec-7-ene was not used. The mold releasability was evaluated. In addition, the normal physical properties and oil resistance of the obtained molded product were measured. The results are shown in Table 2.

The symbols in Table 2 represent the following compounds, and the other compounds represent the same compounds as in Table 1.

N: tetrafluoroethylene / perfluoropropyl vinyl ether / ethylene / 1,4-hexadiene copolymer, O: trimethallyl isocyanurate,
P: 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, Q: calcium hydroxide.

[0060]

[Table 2]

[0061]

The peroxide-crosslinkable fluororubber composition of the present invention is excellent in mold releasability during molding. A molded product obtained by cross-linking and molding this fluororubber composition has excellent heat resistance and oil resistance. Especially, it has excellent durability against high-performance engine oil.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/50 C08K 5/50 // B29K 19:00 B29K 19:00 105: 24 105: 24 F term ( (Reference) 4F071 AA20X AA26 AA27X AC08 AC12 AC15 AE02 AE03 BA01 BC07 4F204 AA16 AA45 AB19 AH16 AH17 FA01 FB01 FF01 4J002 BD121 BD151 EK036 EK046 EK056 EK086 EN027 EN037 EN117 EN138 EU029 EU137 EU029 EN117 EN138 EU029 EU137

Claims (8)

[Claims] 1. A fluororubber containing a vinylidene fluoride-free polymerized unit (A), an organic peroxide (B), and an amine compound (C) and / or an organic onium compound (D). A composition, the fluororubber (A):
The mass ratio of organic peroxide (B): amine compound (C) and / or organic onium compound (D) is 100: 0.3 to 1.
A peroxide-crosslinkable fluororubber composition, which is 0: 0.01 to 5. 2. The peroxide-crosslinkable fluororubber composition composition according to claim 1, wherein the fluororubber (A) is a tetrafluoroethylene / propylene copolymer. 3. The peroxide-crosslinkable fluororubber composition composition according to claim 1, wherein the amine compound (C) is 1,8-diazabicyclo [5.4.0] undec-7-ene. object. 4. The organic onium compound (D) is R ¹ R
² R ³ R ⁴ NOH (wherein R ¹ , R ² , R ³ and R ⁴
Are the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms. ) Organic quaternary ammonium hydroxide (d1) and R ⁵ R ⁶ R ⁷ R ⁸ NHSO ₄ (wherein
R ⁵ , R ⁶ , R ^{7 and} R ⁸ are the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms. ) The organic fourth represented by
The one or more organic onium compounds selected from the group consisting of primary ammonium hydrogen sulfate (d2).
The peroxide-crosslinkable fluororubber composition composition described in 1. 5. The peroxide crosslink according to claim 4, wherein the organic quaternary ammonium hydroxide (d1) is one or more selected from the group consisting of tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide. Fluororubber composition composition. 6. The organic quaternary ammonium hydrogen sulfate (d)
The peroxide-crosslinkable fluororubber composition composition according to claim 4, wherein 2) is tetrabutylammonium hydrogen sulfate. 7. The peroxide crosslinking property according to claim 1, wherein the fluororubber composition contains a crosslinking aid in an amount of 0.3 to 10 parts by mass based on 100 parts by mass of the fluororubber. Fluororubber composition composition. 8. A molded product obtained by molding and crosslinking the peroxide-crosslinkable fluororubber composition composition according to any one of claims 1 to 7.