Fluororubber composition and fluororubber sealing material

Abstract

Provided are a fluororubber composition maintaining rubber properties and excellent in flowability and mold releasability as well as capable of reducing a cross-linking time when molded, and a fluororubber sealing material formed of the fluororubber composition. The fluororubber composition contains a polyol cross-linkable based fluororubber; an aliphatic acid amide based compound; at least one member selected from a phosphoric acid ester based compound, an aliphatic acid ester based compound and a fluorine-containing based compound; and a polyol based cross-linking agent. The fluororubber sealing material is formed of the fluororubber composition.

Claims

1. A fluororubber composition, comprising: a polyol cross-linkable based fluororubber, an aliphatic acid amide-based compound, an aliphatic acid ester-based compound, and a polyol-based cross-linking agent, wherein a total content of the aliphatic acid amide-based compound and the aliphatic acid ester-based compound is 0.5-5.0 parts by mass per the polyol cross-linkable based fluororubber of 100 parts by mass.

2. The fluororubber composition according to claim 1, wherein: a content of the aliphatic acid amide-based compound is 0.01-2.5 parts by mass per the polyol cross-linkable based fluororubber of 100 parts by mass.

3. The fluororubber composition according to claim 1, wherein: a content of the aliphatic acid ester-based compound ranges from 0.1-3.5 parts by mass per the polyol cross-linkable based fluororubber of 100 parts by mass.

4. A fluororubber sealing material formed of the fluororubber composition according to claim 1.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) Hereinafter, embodiments of the present invention will be described in detail. However, a scope of the present invention is not limited to those embodiments shown as examples described below.

(2) The present inventors have focused on dimension stability, mold releasability and a cross-linking rate among the characteristics of the processability demanded for the fluororubber composition. Here, it is difficult to apply only a single type of process aid to the improvement in those plurality types of characteristics. Therefore, the present inventors have examined how to solve the above described disadvantages. That is, such examinations have been carried out by selecting process aids that effectively improve the above respective characteristics and do not deteriorate the rubber properties, and then by using a plurality of the selected process aids in combination.

(3) Here, an aliphatic acid amide based compound is effective for improving the mold releasability and cross-linking rate at the time of molding. However, such an aliphatic acid amide based compound is not always effective for improving dimension stability of a cross-linked molded article associated with flowability. Therefore, it has been required to select process aids that not only improve the dimension stability but also little affect the rubber properties. Eventually, examinations of various process aids having such performance have resulted in findings that a phosphoric acid ester compound, an aliphatic acid ester compound and a fluorine-containing based compound are effective for the improvement.

(4) It should noted that independent use of the phosphoric acid ester based compound, aliphatic acid ester based compound and fluorine-containing based compound cannot improve the processability of the fluororubber composition in a good balance. By contrast, combinational use of those compounds with the aliphatic acid amide compound can exert a synergistic effect, allowing the rubber properties of the fluororubber composition to be maintained and the processability to be simultaneously improved in a good balance.

(5) The fluororubber composition of the present invention includes the polyol cross-linkable based fluororubber; the aliphatic acid amide based compound; at least one member selected from the phosphoric acid ester based compound, aliphatic acid ester based compound and fluorine-containing based compound; and the polyol based cross-linking agent.

(6) Next, each of the materials forming the fluororubber composition will be described more specifically.

(7) (Polyol Cross-Linkable Based Fluororubber)

(8) A polyol cross-linkable based fluororubber is a fluororubber cross-linkable by a polyol based cross-linking agent. A polymer or a co-polymer of one type or two or more types of fluorine-containing olefin monomers may be used for a polyol cross-linkable based fluororubber. The fluorine-containing olefin monomer includes, for example, vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoroacrylic acid ester, acrylic acid perfluoroalkyl ester, perfluoromethyl vinyl ether, and perfluoropropyl vinyl ether or the like. Generally, a polyol cross-linked fluororubber is excellent in the heat-resistance and compression set.

(9) General examples of the polyol cross-linkable fluororubber include, for example, vinylidene fluoride-hexafluoropropylene 2 dimensional co-polymer (an abbreviation: VDF-HFP), tetrafluoroethylene-propylene 2 dimensional co-polymer (an abbreviation: TFE-P), vinylidene fluoride hexafluoropropylene-tetrafluoroethylene 3 dimensional co-polymer (an abbreviation: VDF-HFP-TFE) or the like. Those fluororubbers can be obtained by the methods known in the prior art such as solution polymerization, suspension polymerization or emulsion polymerization, and available as a commercial product (e.g., Viton® A500, DuPont).

(10) (Aliphatic Acid Amide Based Compound)

(11) An aliphatic acid amide based compound is used as a lubricant for a rubber composition. Examples of the aliphatic acid amide based compound include lauric amide, stearic amide, oleic amide, behenic amide, erucic amide, methylene bisstearylamide, ethylene bisstearylamide, ethylene bisoleylamide, hexamethylene bisstearylamide, and palmitic amide.

(12) Preferably, a content of the aliphatic acid amide based compound is set to 0.01˜2.5 parts by mass per the polyol cross-linkable fluororubber of 100 parts by mass, more preferably 0.1˜1.5 parts by mass. When the content is in the range, it is possible to add an improvement in appropriate mold releasability and an increase in a cross-linking rate to the fluororubber composition.

(13) (Phosphoric Acid Ester Based Compound)

(14) A phosphoric acid ester based compound is used as a plasticizer for a rubber composition. Examples of the phosphoric acid ester based compound include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tributoxyethyl phosphate, 2-ethylhexyl phosphate, tricresyl phosphate, polyoxyethylene stearyl ether phosphate or the like.

(15) (Aliphatic Acid Ester Based Compound)

(16) An aliphatic acid ester based compound is used as a lubricant for a rubber composition. Examples of the aliphatic acid ester based compound include methyl laurate, methyl stearate, methyl oleate, isopropyl myristate, isopropyl palumitate, butyl palumitate, butyl stearate, 2-ethylhexyl palumitate, 2-ethylhexyl oleate, pentaerythritol stearate, and myricyl cerotate or the like.

(17) (Fluorine-Containing Based Compound)

(18) A fluorine-containing based compound is used as a lubricant and a mold release agent for a rubber composition. Examples of the fluorine-containing based compound include polytetrafluoroethylene (PTFE), ethylene/tetrafluoroethylene co-polymer (ETFE), polyfluorovinylidene (PVdF), and perfluoroalkyl ether or the like.

(19) A total content of the aliphatic acid amide based compound, phosphoric acid ester based compound, aliphatic acid ester based compound and fluorine-containing based compound is preferably set to 0.5˜5.0 parts by mass per the polyol cross-linkable based fluororubber of 100 parts by mass, more preferably 0.5˜4.0 parts by mass. When the total content is in the range, it is possible to provide the fluororubber composition with an improvement in the appropriate mold releasability, increase in the cross-linking rate and improvement in the dimension stability in a god balance.

(20) When the polyol cross-linkable based fluororubber includes the phosphoric acid ester based compound, the aliphatic acid ester based compound or the fluorine-containing based compound, respective contents thereof are preferably set to 0.1˜3.5 parts by mass per the polyol cross-linkable based fluororubber of 100 parts by mass, more preferably 0.3˜2.5 parts by mass. When the respective contents are in the range, it is possible to add appropriate improvement in dimension stability to the fluororubber composition.

(21) Preferably, a total content of the phosphoric acid ester based compound, aliphatic acid ester based compound and fluorine-containing based compound is set to 0.3˜5.0 parts by mass per the polyol cross-linkable fluororubber of 100 parts by mass, more preferably 0.5˜3.5 parts by mass. When the total content is in the range, it is possible to add appropriate improvement in dimension stability to the fluororubber composition.

(22) (Polyol Based Cross-Linking Agent)

(23) A polyol based cross-linking agents used for cross-linking the polyol cross-linkable based fluororubber preferably includes bisphenol compounds. More specifically, such bisphenol compounds include, for example, polyhydroxy aromatic compounds such as 2,2-bis(4-hydroxyphenyl)propane [Bisphenol A], 2,2-bis(4-hydroxyphenyl)perfluoropropane [Bisphenol AF], bis(4-hydroxyphenyl)sulfone [Bisphenol S], Bisphenol A-bis (di-phenylphosphate), 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl-methane, 2,2-bis(4-hydroxyphenyl)butane. Preferable examples are Bisphenol A and Bisphenol AF or the like. The polyol based cross-linking agent may have a form of alkali metal salt or alkali-earth metal salt. The polyol based cross-linking agent may be blended as a masterbatch mixed with a raw material rubber or the like. A commercially available masterbatch includes, for example, Curative VC #30 (DuPont Dow Elastomers LLC.; including Bisphenol AF at 50 wt %).

(24) A content of the polyol based cross-linking agent is preferably set to 0.4˜20 parts by mass per the polyol cross-linkable based fluororubber 100 parts by mass, more preferably 1˜10 parts by mass. The polyol based cross-linking agent may be blended as a masterbatch mixed with a raw material rubber or the like.

(25) (Fluororubber Composition)

(26) A fluororubber composition of the present embodiment may be appropriately blended further with known additives in the range that does not inhibit the effects of the present embodiment, as necessary. For example, such additives include a cross-linking promoter, a cross-linking aid, a cross-linking promoter aid, a rubber reinforcer, a filler, a plasticizer, a softener, an antioxidant agent, a process aid, a foaming agent, a foaming agent aid, a coloring agent, a dispersion agent, a flame retardant, a tackifier, a mold release agent, powder of various types of metals, a thermoplastic resin, a rubber and short fibers or the like.

(27) As for a cross-linking promoter, used are a quarternary ammonium salt and a quarternary phosphonium salt and so on. The quarternary ammonium salt includes, for example, 5-benzyl-1,5-diazabicyclo [4.3.0]-5-nonenium tetrafluoroborate, 8-methyl-1,8-diazabicyclo [5.4.0]-7-undecenium chloride, 8-ethyl-1,8-diazabicyclo[5.4.0]-7-undecenium bromide or the like. The quarternary phosphonium salt includes, for example, tetraphenylphosphonium chloride, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, triphenylmethoxymethylphosphonium chloride, triphenylmethylcarbonylmethylphosphonium chloride, trioctylbenzylphosphonium chloride, trioctylmethylphosphonium bromide, trioctylethylphosphonium acetate, trioctylethylphosphonium dimethylphosphate, tetraoctylphosphonium chloride, cetyldimethylbenzylphosphonium chloride or the like.

(28) Any production device known in the prior art may be used for manufacturing the fluororubber composition. More specifically, used are a closed type kneading device such as a kneader, a Banbury mixer, an intermix, a planetarium mixer and an open type kneading device such as an open roll mill.

(29) (Molding of Fluororubber Composition)

(30) Any production device known in the prior art may be used for producing a cross-linked molded article by molding and cross-linking the fluororubber composition. Specifically, the fluororubber composition is charged inside a cavity with a predetermined shape by using an injection molding device, a compression molding device or a cross-linking press machine. Then, the composition is thermally cross-linked under appropriate conditions to produce a cross-linked molded article. As necessary, the resulting article is further subjected to a second cross-linking process.

(31) The fluororubber composition of the present embodiment may be used for various applications. For example, such applications include various types of sealing materials (e.g., O-ring, packing, gasket and diaphragm), a hose, an anti-vibration rubber and a belt. Among those various applications, a sealing material is a representative one capable of exerting the advantageous effects of the present embodiment.

EXAMPLES

(32) Hereinafter, the present invention will be described more specifically referring to Examples and Comparative Examples. However, the present invention is not limited to those Examples.

(33) (Raw Materials of Fluororubber Composition)

(34) The following materials were used for raw materials of the fluororubber composition.

(35) Polyol Cross-linkable Based Fluororubber: Vinylidene fluoride-hexafluoropropylene 2 dimensional co-polymer, 3M, Dyneon® FC2230.

(36) Cross-linking Agent: Polyol based cross-linking agent, Tokyo Chemical Industry Co., Ltd., Bisphenol AF.

(37) Cross-linking Promoter: Quarternary phosphonium salt masterbatch, DuPont, Curative VC #20.

(38) Cross-linking Aid: Magnesium oxide, Kyowa Chemical Industry Co., Ltd., Kyowamag® #150.

(39) Cross-linking Promoter Aid: Calcium hydroxide, Ohmi Chemical Industry Co., Ltd., CALDIC® #2000.

(40) Rubber Reinforcer: Carbon black, thermal black, Cancarb Limited, N990.

(41) Process Aid:

(42) (i) Aliphatic acid amide based compound: Nihon Kasei Co., Ltd., Sripacks L.

(43) (ii) Aliphatic acid amide based compound: Tokyo Chemical Industry Co., Ltd., Oleic Amide.

(44) (iii) Phosphoric acid ester based compound: TOHO Chemical Industry Co., Ltd., RL210.

(45) (iv) Aliphatic acid ester based compound: DuPont, VPA #2.

(46) (v) Aliphatic acid ester based compound: King Industries, Deoflow 821.

(47) (vi) Fluorine-containing based compound: Solvay, FPA1.

(48) (vii) Fluorine-containing based compound: Daikin Industries, Ltd., FB962.

(49) (viii) Natural Wax/Aliphatic Acid/Alkylamine/Hydrocarbon Based Resin Compound: Structol, HT290.

(50) (ix) Aliphatic acid metal salt based compound: Kao Corporation, NS-Soap.

(51) (Production of Fluororubber Composition)

(52) In the formulation listed in Table 1 or Table 2, a mixture was kneaded at 100° C. or less for 10˜30 min using a 1 L kneader or an open roll kneader. Then, the mixture was passed through an open roll thereby to prepare an uncross-linked rubber sheet. Here, an attainable temperature of the 1 L kneader was 90° C. Using the uncross-linked rubber sheet thus obtained, cross-linking characteristics described in JIS K6300-2:2001 at 180° C. were measured.

(53) Further, an uncross-linked rubber composition was cross-linked and molded (i.e., first cross-linking) into a shape of the bearing number G25 of a fixing O-ring described in JIS B2401-1:2012 by using a press molding machine under the conditions of 180° C.×6 min. After that, the resulting molded product was subjected to a post curing process under the conditions of 230° C.×24 hr. The resulting O-ring thus obtained was evaluated in compression set. Moreover, each of the following items was evaluated (i.e., Examples 1˜7, Comparative Examples 1˜8).

(54) (Cross-Linking Time)

(55) A 90% cross-linking time t90 (sec) at 180° C. was measured via conforming to JIS K6300-2:2001. Specifically, a difference in cross-linking times (sec) of each sample piece was calculated by subtracting a value of t90 when adding no process aid from a value of t90 when adding the aid. That is, in case of Examples 1˜7 and Comparative Examples 2˜8, a difference in cross-linking times (sec) was calculated by subtracting the value (i.e., 195) of t90 in Comparative Example 1 from each value of t90(s) in Examples 1˜7 and Comparative Examples 2˜8.

(56) When a difference in cross-linking times was a negative value smaller than −10 (sec), this condition exerted an effect for increasing the cross-linking rate, resulting in the evaluation of Good.

(57) By contrast, when a difference in cross-linking times was a negative value equal to or larger than −10 (sec), this condition exerted no or little effect for increasing the cross-linking rate, resulting in the evaluation of Poor.

(58) (Dimension Stability)

(59) An O-ring in a shape of the bearing number G25 of a fixing O-ring was molded via conforming to JIS B2401-1:2012. The resulting O-ring was subjected to a post curing process under the conditions of 230° C.×24 hr. A mean diameter of the O-ring was calculated by measuring diameters of the molded article (n=3). When the mean diameter of the O-ring was in the range of 3.1±0.05 mm, the dimension stability was determined as Good, while otherwise the dimension stability was determined as Poor.

(60) (Mold Releasability)

(61) Mold Releasability: Using a mold with 2×5 cavities in the G25 shape, mold releasability of an O-ring when molded by compression press was evaluated based on the following criteria.

(62) Good: When an O-ring was released, the resistance was small, it was integrally released, and no cut-lines occurred between the product and burrs.

(63) Poor: When an O-ring was released, cut-lines occurred between the product and burrs.

(64) (Compression Set)

(65) A compression set as rubber properties was evaluated by using a cross-linked O-ring. An O-ring in the G25 shape was 2-point cut to prepare semi-circular sample pieces each having a diameter of about 3.1 mm. The sample piece was sandwiched between SUS plates and put into an oven at 175° C. in the 25% compressed condition. Immediately after heated for 70 hr, the sample piece was released from the SUS plates and left at room temperature for 30 min. A compression set of the sample piece was calculated by a change in diameters before and after the experiment. Herein, an experimental method and calculating method were conducted via conforming to JIS K6262: 2013.

(66) As for each sample piece, a difference (%) in compression sets was calculated by subtracting a value of a compression set when adding no process aid to the formulation from a value of a compression set when adding it. That is, in case of Examples 1˜7 and Comparative Examples 2˜8, a value was calculated by subtracting a value (i.e., 12) of the compression set in Comparative Example 1 from each value of the compression sets in others. When a difference in the compression sets was small than +5(%), the compression set of the sample piece was determined as Good. By contrast, when a difference in the compression sets was equal to or larger than +5(%), the compression set of the sample piece was determined as Poor.

(67) TABLE-US-00001 TABLE 1 EX. 1 1 EX.2 EX. 3 EX.4 EX.5 EX.6 EX.7 Formulation Fluororubber Polyol Cross-Likable Dyneon Parts By 100 100 100 100 100 100 100 2-D Fluororubber FC2230 Mass Rubber Carbon Black N990 Parts By 35 35 35 35 35 35 35 Reinforcer Mass Cross Linking Polyol Based Bisphenol AF Parts By 2 2 2 2 2 2 2 Agent Cross-Linking Mass Cross-Linking Quaternary Phosphonium VC#20 Parts By 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Promoter Salt Based Masterbatch Mass Cross-Linking Magnesium Oxide Kyowamag Parts By 3 3 3 3 3 3 3 Aid #150 Mass Cross-Linking Calcium Hydroxide CALDIC Parts By 5 5 5 5 5 5 5 Promoter Aid #2000 Mass Process Aid Aliphatic Acid Amide Sripacks L Parts By 0.6 0.6 — — — 0.3 — Based Compound Mass Aliphatic Acid Amide Oleic Amide Parts By — — 0.2 0.2 0.2 0.1 0.2 Based Compound Mass Phosphoric Acid Ester RL210 Parts By — — — — 0.7 — — Based Compound Mass Aliphatic Acid Ester VPA#2 Parts By 1.0 — 1.0 — — 0.5 — Based Compound Mass Aliphatic Acid Ester Deoflow 821 Parts By — 1.5 — — — — — Based Compound Mass Fluorine-Comtaining FPA1 Parts By — — 1.5 1.5 — — 1.5 Based Compound Mass Fluorine-Containing FB962 Parts By — — — — — 0.5 — Based Compound Mass Natural Wax/Aliphatic Acid/Alkylamine/ HT290 Parts By — — — — — 0.2 — Hydrocarbon Based Mass Compound Aliphatic Acid Metal Salt NS-Soap Parts By — — — — — — 0.2 Based Compound Mass Evaluation of Cross-Linkability Difference in sec −16 −22 −13 −15 −11 −18 −18 Peformance Cross-Linking Dimension Diameter of G25 O-Ring mm 3.14 3.15 3.11 3.13 3.14 3.13 3.11 Stability Mold Mold Releasability When Good Good Good Good Good Good Good Releasability Molding G25 O-Ring Rubber Properties Compression Set % +4 +4 +4 +2 +3 +4 +4

(68) TABLE-US-00002 TABLE 2 COM. COM. COM. COM. COM. COM. COM. COM. EX. 1 EX. 2 EX. 3 EX. 4 EX. 5 EX. 6 EX. 7 EX. 8 Form- Fluororubber Polyol Cross- Dyneon Parts By 100 100 100 100 100 100 100 100 ulation Linkable 2-D PC2230 Mass Fluororubber Rubber Carbon Black N990 Parts By 35 35 35 35 35 35 35 35 Reinforcer Mass Cross-Linking Polyol Based Bisphenol Parts By 2 2 2 2 2 2 2 2 Agent Cross-Linking AF Mass Agent Cross-Linking Quaternary VC#20 Parts By 1.5 1.5 1 5 1.5 1.5 1.5 1.5 1.5 Promoter Phosphonium Mass Salt Based Masterbatch Cross-Linking Magnesium Oxide Kyowamag Parts By 3 3 3 3 3 3 3 3 Aid #150 Mass Cross-Linking Calcium CALDIC Parts By 5 5 5 5 5 5 5 5 Promoter Aid Hydroxide #2000 Mass Process Aid Aliphatic Acid Sripacks L Parts By — 1.5 — — — — — — Amide Based Mass Compound Aliphatic Acid Oleic Parts By — — — — — — 0.5 — Amide Based Amide Mass Compound Phosphoric Acid RL210 Parts By — — — — 1.5 — — — Ester Based Mass Compound Aliphatic Acid VPA#2 Parts By — — 1.5 — — — — — Ester Based Mass Compound Aliphatic Acid Deoflow Parts By — — — — — — — — Ester Based 821 Mass Compound Fluorine- FPA1 Parts By — — — 1.5 — — — — Containing Based Mass Compound Fluorine-Contaning FB962 Parts By — — — — — — — — Based Compound Mass Natural Wax/ HT290 Parts By — — — — — 1.5 1.5 — Aliphatic Acid/ Mass Alkylamine/ Hydrocarbon Based Compound Aliphatic Acid NS-Soap Parts By — — — — — — — 1.5 Metal Salt Mass Based Compound Eval- Cross- Difference in sec (195) −25 +10 +5 +11 +13 −5 −24 uation Linkability Cross-Linking of Times Perfor- Dimension Diameter of G25 mm 3.17 3.18 3.15 3.14 3.13 3.12 3.13 3.18 mance Stability O-Ring Mold Mold Releasability Poor Good Poor Poor Good Poor Poor Poor Releasability When Molding G25 O-Ring Rubber Compression Set % (12) +5 +4 +2 +5 +11 +10 +8 Properties

(69) As shown by the evaluation results in Tables 1 and 2, all the Examples 1˜7 were excellent in the cross-linkability, dimension stability, mold releasability and rubber properties. By contrast, Comparative Examples 1˜8 did not satisfy the requirements of the claims, resulting in poor performance on at least one of the cross-linkability, dimension stability, mold releasability and rubber properties.