EP0733085A1 - Peroxide-crosslinkable, low-hardness, fluorine rubber composition - Google Patents

Peroxide-crosslinkable, low-hardness, fluorine rubber composition

Info

Publication number
EP0733085A1
EP0733085A1 EP95904842A EP95904842A EP0733085A1 EP 0733085 A1 EP0733085 A1 EP 0733085A1 EP 95904842 A EP95904842 A EP 95904842A EP 95904842 A EP95904842 A EP 95904842A EP 0733085 A1 EP0733085 A1 EP 0733085A1
Authority
EP
European Patent Office
Prior art keywords
weight
fluoroelastomer
parts
peroxide
hardness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95904842A
Other languages
German (de)
French (fr)
Inventor
Fumio Sugeno
Hiroshi Saito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0733085A1 publication Critical patent/EP0733085A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

  • the present invention relates to a novel vulcanization composition containing a fluoroelastomer. More specifically, the present invention is directed to a peroxide-vulcanizable fluoroelastomer composition which permits achievement of low hardness and excellent chemical resistance. BACKGROUND OF THE INVENTION
  • Fluoroelastomers have excellent heat resistance and oil resistance. Therefore, they are used for O-rings, gaskets, oil seals, diaphragms, hoses, rolls, sheet materials, and the like in a variety of industrial fields, such as those involving automobiles, ships, aircraft, and hydraulic devices; the chemical industry and general appliances industry; and pollution-related fields.
  • Peroxide-vulcanizable fluoroelastomer products have exceptional acid and chemical resistance and are used for office equipment, in the fields of medical drugs and medical treatment, and in food product-related applications. Peroxide-vulcanized fluoroelastomer products having a low degree of hardness are desirable for applications which require acid or chemical resistance as well as good sealing properties with low tightening force in glass or plastic vessels. However, there are no examples of any such products which are satisfactory in terms of practical performance with a hardness of 50 or less.
  • the present invention is a peroxide-vulcanizable fluoroelastomer composition which allows a molded article with a hardness of 50 or less to be obtained, which composition comprises a) a peroxide-vulcanizable bromine-containing fluoroelastomer or iodine-containing fluoroelastomer, said fluoroelastomer having i) at least 20% by weight of a fraction having molecular weight of no more than 50,000, and ii) no more than 1% by weight of a fraction having molecular weight of 1,000,000 or more; b) 0.1 to 5 parts by weight of an organic peroxide per 100 parts by weight of a); and c) 0.1 to 5 parts by weight of a poly functional co-crosslinker per 100 parts by weight of a).
  • the present invention provides a peroxide-vulcanizable fluoroelastomer composition which permits a molded article with a hardness of 50 or less to be obtained without impairing the kneading workability and without sacrificing the heat resistance, oil resistance, acid resistance, and chemical resistance which are characteristic of conventional peroxide-vulcanizable fluoroelastomers.
  • component a) of the present invention examples include binary copolymers having interpolymerized units of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), or ternary copolymers having interpolymerized units of VDF, HFP, and tetrafluoroethylene (TFE), either of which copolymers contain bromine and/or iodine in the polymer chain or polymer terminals.
  • VDF vinylidene fluoride
  • HFP hexafluoropropylene
  • TFE tetrafluoroethylene
  • binary and ternary refer to principal constituent monomers which do not include interpolymerized units of bromine-containing or iodine-containing monomers.
  • Component b) of the present invention is an organic peroxide that produces peroxide radicals at the vulcanization temperature, for example, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- di-(t-butylperoxy) hexane, and 2,5-dimethyl-2,5-2,5-di-(t-butylperoxy) hexane-3.
  • Component c) is a polyfunctional co-crosslinker.
  • Examples of component c) of the present invention include triallylcyanurate, triallylisocyanurate, and trimethallylisocyanurate.
  • the ratio in which component b) is used is 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight, per 100 parts by weight of component a) of the present invention.
  • Component c) is used in a ratio of 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight per 100 parts by weight of component a).
  • Use of less than 0.1 weight part of component b) does not permit the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 parts by weight does not permit a hardness of 50 or less to be achieved.
  • Use of less than 0.1 parts by weight of component c) does not allow the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 weight parts makes it difficult to achieve a hardness of 50 or less.
  • the molecular weight distribution of component a) is stipulated within the aforementioned range because less than 20% by weight of the M50 fraction does not allow a hardness of 50 or less to be achieved. Similarly, more than 1% by weight of the Ml 000 fraction also does not allow a hardness of 50 or less to be achieved.
  • Other components such as carbon black, Austin black, graphite, silica, clay, diatomaceous earth, talc, calcium carbonate, calcium silicate, calcium sulfate, fatty acid calcium, fatty acid amides, low molecular weight polyethylene, silicone oil, silicone grease, metal soap, stearic acid, fatty amines, titanium oxide, red iron oxide, and other such fillers, working adjuvants, plasticizers, coloring agents, and the like can be blended as needed into the fluoroelastomer composition of the present invention.
  • Acid-absorbers such as magnesium oxide, zinc oxide, calcium oxide, and calcium hydroxide, may also be added.
  • Methods for vulcanizing the fluoroelastomer composition thus obtained include methods in which the material is kneaded using an open-type mixing roll or closed-type kneading roll (such as a Banbury mixer or a pressure kneader), and the material is then introduced into a heated mold and compressed to effect primary vulcanization, followed by secondary vulcanization.
  • an open-type mixing roll or closed-type kneading roll such as a Banbury mixer or a pressure kneader
  • the conditions for the primary vulcanization include a temperature of 120° to 200°C, a time of 1 to 80 minutes, and a pressure of 20 to 150 kg/cm 2
  • the conditions for the secondary vulcanization include a temperature of 120° to 250°C, and a time of 0 to 48 hours.
  • Other vulcanization means which can be used include methods in which a preform is fashioned by injection or extrusion or the like, followed by vulcanization, or methods in which one or more ketones, ethers, or the like are used as media to prepare a solution or dispersion, which is then used to coat the surface of paper, fiber, film, sheets, plates, tubes, pipes, tanks, large-scale containers, or other molded articles, followed by vulcanization.
  • Liquid chromatograph model LC-3A (Shimadzu Seisakusho) Columns: KF-80 M (two) & KF-800 P (precolumn) (Showa Denko) Detector: ERC-7510 S (Elmer Optical)
  • Polymer serving as standard for molecular weight detection lines various types of monodisperse polystyrene (Toyo Soda) Concentration: 0.1 wt%
  • Fluoroelastomer FR-6150 (100 parts by weight, 34% by weignt M50 fraction and 0% Ml 000 fraction) manufactured by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol% HFP, 17.4 mol% TFE, 68.0 wt% F content, and 5200 ppm I content) was wound on an open-type mixing roll. Carbon black (3 parts by weight, Thermax N-990 from Cancarb), 1 part by weight lead oxide (Litharge No.
  • Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1 part by weight and the amount of TAIC used was 2 parts by weight. The various tests were conducted, and the results are shown in Table 1.
  • Example 3 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1.5 parts by weight and the amount of TAIC used was 3 parts by weight. The various tests were conducted, and the results are shown in Table 1.
  • Comparative Example 1 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by FR-6350 (containing 13% M50 and 0% M1000) by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol % HFP, 17.4 mol % TFE, 68.0% F content, and 3000 ppm I content). The various tests were conducted. The results are shown in Table 1.
  • Comparative Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by G-902 (containing 21% M50 and 1.5% Ml 000) by Daikin Industries (54.7 mol% VDF, 23.6 mol% HFP, 21.7 mol% TFE, 69.7% F content, and 2200 ppm I content). The various tests were conducted. The results are shown in Table 1.
  • Vulcanizability (g). 160°C Optimal time (min) 10.8 11.0 11.5 12.5 11.8

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Peroxide-vulcanizable fluoroelastomer compositions yield molded articles with a hardness of 50 or less.

Description

TITLE
PEROXIDE-CROSSLINKABLE, LOW-HARDNESS,
FLUORINE RUBBER COMPOSITION
FIELD OF THE INVENTION The present invention relates to a novel vulcanization composition containing a fluoroelastomer. More specifically, the present invention is directed to a peroxide-vulcanizable fluoroelastomer composition which permits achievement of low hardness and excellent chemical resistance. BACKGROUND OF THE INVENTION
Fluoroelastomers have excellent heat resistance and oil resistance. Therefore, they are used for O-rings, gaskets, oil seals, diaphragms, hoses, rolls, sheet materials, and the like in a variety of industrial fields, such as those involving automobiles, ships, aircraft, and hydraulic devices; the chemical industry and general appliances industry; and pollution-related fields.
Peroxide-vulcanizable fluoroelastomer products have exceptional acid and chemical resistance and are used for office equipment, in the fields of medical drugs and medical treatment, and in food product-related applications. Peroxide-vulcanized fluoroelastomer products having a low degree of hardness are desirable for applications which require acid or chemical resistance as well as good sealing properties with low tightening force in glass or plastic vessels. However, there are no examples of any such products which are satisfactory in terms of practical performance with a hardness of 50 or less.
There have been studies directed to lowering the hardness of peroxide-vulcanizable fluoroelastomers. In the method disclosed in Japanese Laid-Open Patent Application 62-277456, for example, a liquid fluorine rubber is blended in a solid fluorine rubber in a ratio of 100:10 to 100: 100 to effect peroxide vulcanization so as to obtain a molded article having a hardness of 53 to 57. The addition of large amounts of the liquid fluorine rubber in this method, however, results in poor kneading workability, and it is still not possible to obtain a molded article with a hardness of 50 or less. SUMMARY OF THE INVENTION
The present invention is a peroxide-vulcanizable fluoroelastomer composition which allows a molded article with a hardness of 50 or less to be obtained, which composition comprises a) a peroxide-vulcanizable bromine-containing fluoroelastomer or iodine-containing fluoroelastomer, said fluoroelastomer having i) at least 20% by weight of a fraction having molecular weight of no more than 50,000, and ii) no more than 1% by weight of a fraction having molecular weight of 1,000,000 or more; b) 0.1 to 5 parts by weight of an organic peroxide per 100 parts by weight of a); and c) 0.1 to 5 parts by weight of a poly functional co-crosslinker per 100 parts by weight of a). DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a peroxide-vulcanizable fluoroelastomer composition which permits a molded article with a hardness of 50 or less to be obtained without impairing the kneading workability and without sacrificing the heat resistance, oil resistance, acid resistance, and chemical resistance which are characteristic of conventional peroxide-vulcanizable fluoroelastomers. It has been discovered that the aforementioned objectives can be achieved by provision of a composition obtained by blending a prescribed amount of an organic peroxide and a prescribed amount of a polyfunctional co-crosslinker with a peroxide-vulcanizable fluoroelastomer containing at least 20% by weight of a fraction having molecular weight of no more than 50,000 (hereinafter abbreviated as M50) and no greater than 1% by weight of a fraction having molecular weight of 1,000,000 or more (hereinafter abbreviated as Ml 000). It can thus be used in applications in the fields of office equipment, food products, medical drugs, and medical treatment instruments.
Examples of component a) of the present invention include binary copolymers having interpolymerized units of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), or ternary copolymers having interpolymerized units of VDF, HFP, and tetrafluoroethylene (TFE), either of which copolymers contain bromine and/or iodine in the polymer chain or polymer terminals. As used herein, "binary" and "ternary" refer to principal constituent monomers which do not include interpolymerized units of bromine-containing or iodine-containing monomers. Iodine or bromine is introduced into the polymer chain either by use of chain transfer agents or by copolymerization of bromine- or iodine-containing olefin monomers. Methods for manufacture of such polymers have been disclosed, for example, in Japanese Patent Application 59-7513. Component b) of the present invention is an organic peroxide that produces peroxide radicals at the vulcanization temperature, for example, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- di-(t-butylperoxy) hexane, and 2,5-dimethyl-2,5-2,5-di-(t-butylperoxy) hexane-3.
Component c) is a polyfunctional co-crosslinker. Examples of component c) of the present invention include triallylcyanurate, triallylisocyanurate, and trimethallylisocyanurate.
The ratio in which component b) is used is 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight, per 100 parts by weight of component a) of the present invention. Component c) is used in a ratio of 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight per 100 parts by weight of component a). Use of less than 0.1 weight part of component b) does not permit the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 parts by weight does not permit a hardness of 50 or less to be achieved. Use of less than 0.1 parts by weight of component c) does not allow the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 weight parts makes it difficult to achieve a hardness of 50 or less.
The molecular weight distribution of component a) is stipulated within the aforementioned range because less than 20% by weight of the M50 fraction does not allow a hardness of 50 or less to be achieved. Similarly, more than 1% by weight of the Ml 000 fraction also does not allow a hardness of 50 or less to be achieved.
Other components, such as carbon black, Austin black, graphite, silica, clay, diatomaceous earth, talc, calcium carbonate, calcium silicate, calcium sulfate, fatty acid calcium, fatty acid amides, low molecular weight polyethylene, silicone oil, silicone grease, metal soap, stearic acid, fatty amines, titanium oxide, red iron oxide, and other such fillers, working adjuvants, plasticizers, coloring agents, and the like can be blended as needed into the fluoroelastomer composition of the present invention. Acid-absorbers, such as magnesium oxide, zinc oxide, calcium oxide, and calcium hydroxide, may also be added. One or two conventionally known vulcanization agents or vulcanization promoters may also be added, provided that the essence of the present invention is not thereby compromised. Methods for vulcanizing the fluoroelastomer composition thus obtained include methods in which the material is kneaded using an open-type mixing roll or closed-type kneading roll (such as a Banbury mixer or a pressure kneader), and the material is then introduced into a heated mold and compressed to effect primary vulcanization, followed by secondary vulcanization. The conditions for the primary vulcanization include a temperature of 120° to 200°C, a time of 1 to 80 minutes, and a pressure of 20 to 150 kg/cm2, and the conditions for the secondary vulcanization include a temperature of 120° to 250°C, and a time of 0 to 48 hours. Other vulcanization means which can be used include methods in which a preform is fashioned by injection or extrusion or the like, followed by vulcanization, or methods in which one or more ketones, ethers, or the like are used as media to prepare a solution or dispersion, which is then used to coat the surface of paper, fiber, film, sheets, plates, tubes, pipes, tanks, large-scale containers, or other molded articles, followed by vulcanization.
EXAMPLES The present invention is described in further detail below with reference to certain preferred embodiments wherein all parts are by weight unless otherwise specified. The molecular weight distribution of the fluoroelastomer and the physical properties, etc., of the vulcanized composition were determined using the following methods. 1) Molecular weight distribution:
Liquid chromatograph: model LC-3A (Shimadzu Seisakusho) Columns: KF-80 M (two) & KF-800 P (precolumn) (Showa Denko) Detector: ERC-7510 S (Elmer Optical)
Integrator: 7000 A (System Instruments) Developing solvent: tetrahydrofuran
Polymer serving as standard for molecular weight detection lines: various types of monodisperse polystyrene (Toyo Soda) Concentration: 0.1 wt%
Temperature: 35°C (2) Physical properties of the vulcanized product: Hardness measured according to JIS A.
100% tensile stress, tensile strength, elongation, and compression set measured according to JIS K 6301.
Example 1
Fluoroelastomer FR-6150 (100 parts by weight, 34% by weignt M50 fraction and 0% Ml 000 fraction) manufactured by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol% HFP, 17.4 mol% TFE, 68.0 wt% F content, and 5200 ppm I content) was wound on an open-type mixing roll. Carbon black (3 parts by weight, Thermax N-990 from Cancarb), 1 part by weight lead oxide (Litharge No. 1 Canary Yellow from Nippon Chemical Industry), 0.5 part by weight 2,5-dimethyl-2,5- di (t-butylperoxy) hexane (Perhexa 2,5 B, from Nippon Oil & Fats), and 1 part by weight triallylisocyanurate (TAIC, from Nippon Chemical Industry) were kneaded and then allowed to age overnight.
The material was kneaded again, introduced into a mold, and press cured for 15 minutes at a temperature of 160°C for molded sheet or press cured for 20 minutes at a temperature of 160°C for molded JIS cylinder. The material was removed from the mold and heated for four hours in a circulating air oven at a temperature of 180°C to complete the secondary vulcanization, and the various tests were conducted. The results are shown in Table 1. Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1 part by weight and the amount of TAIC used was 2 parts by weight. The various tests were conducted, and the results are shown in Table 1.
Example 3 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1.5 parts by weight and the amount of TAIC used was 3 parts by weight. The various tests were conducted, and the results are shown in Table 1.
Comparative Example 1 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by FR-6350 (containing 13% M50 and 0% M1000) by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol % HFP, 17.4 mol % TFE, 68.0% F content, and 3000 ppm I content). The various tests were conducted. The results are shown in Table 1.
Comparative Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by G-902 (containing 21% M50 and 1.5% Ml 000) by Daikin Industries (54.7 mol% VDF, 23.6 mol% HFP, 21.7 mol% TFE, 69.7% F content, and 2200 ppm I content). The various tests were conducted. The results are shown in Table 1.
Table 1. Summary of Formulations and Results
Comp. Comp.
Ex- . Ex. 2 Ex. 3 Ex. 1 Ex. 2
Blend
Ex. 1 Polymer 100 100 100
Comp. Ex. 1 Polymer 100
Comp. Ex. 2 Polymer 100
Thermax N-990 3 3 3 3 3
Litharge No. 1 Yellow 1 1 1 1 1
TAIC 1 2 3 1 1
Perhexa 2,5 B 0.5 1 1.5 0.5 0.5
Vulcanizability (g). 160°C Optimal time (min) 10.8 11.0 11.5 12.5 11.8
Physical Properties (g). 23 °C Hardness (points) 47 48 49 52 53 100% Tensile Stress (kgff cm2) 9 10 11 10 12 Tensile Strength (kgfTcm2) 138 142 145 130 135 Elongation (%) 600 550 500 570 590
Compression Set
25% compression, 150°C, 70 hr 28 23 20 33 30

Claims

CLAIMS:
1. A vulcanizable fluoroelastomer composition, which comprises a) a peroxide-vulcanizable bromine-containing fluoroelastomer or iodine-containing fluoroelastomer, said fluoroelastomer having i) at least 20% by weight of a fraction having molecular weight of no more than 50,000 and ii) no more than 1% by weight of a fraction having molecular weight of 1,000,000 or more; b) 0.1 to 5 parts by weight of an organic peroxide per 100 parts by weight of a); and c) 0.1 to 5 parts by weight of a polyfunctional co-crosslinker per 100 parts by weight of a).
2. The vulcanizable fluoroelastomer composition of Claim 1 , wherein the bromine-containing fluoroelastomer or iodine- containing fluoroelastomer is a binary copolymer having interpolymerized units of vinylidene fluoride and hexafluoropropylene.
3. The vulcanizable fluoroelastomer composition of Claim 1, wherein the bromine-containing fluoroelastomer or iodine- containing fluoroelastomer is a ternary copolymer having interpolymerized units of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene.
4. The vulcanizable fluoroelastomer composition of Claim 1, wherein component b) is present in an amount of 0.3 to 3 parts by weight.
5. The vulcanizable fluoroelastomer composition of Claim 1, wherein the amount of component c) is 0.3 to 3 parts by weight..
EP95904842A 1993-12-07 1994-12-06 Peroxide-crosslinkable, low-hardness, fluorine rubber composition Withdrawn EP0733085A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP30657493A JPH07196878A (en) 1993-12-07 1993-12-07 Low-hardness fluororubber vulcanizing composition crosslinkable by peroxide
JP306574/93 1993-12-07
PCT/US1994/014093 WO1995015995A1 (en) 1993-12-07 1994-12-06 Peroxide-crosslinkable, low-hardness, fluorine rubber composition

Publications (1)

Publication Number Publication Date
EP0733085A1 true EP0733085A1 (en) 1996-09-25

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP95904842A Withdrawn EP0733085A1 (en) 1993-12-07 1994-12-06 Peroxide-crosslinkable, low-hardness, fluorine rubber composition

Country Status (3)

Country Link
EP (1) EP0733085A1 (en)
JP (1) JPH07196878A (en)
WO (1) WO1995015995A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2805705A1 (en) 2013-05-23 2014-11-26 IP Gesellschaft für Management mbH Packaging with one or more administration units comprising a sodium salt of (R)-3-[6-amino-pyridin-3-yl]-2-(1-cyclohexyl-1 H-imidazol-4-yl)-propionic acid

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69826463T2 (en) * 1997-04-15 2005-09-22 Daikin Industries, Ltd. VULCANIZATION MIXTURE FOR FLUORECURA AND FLUOROUS PURPOSE COMPONENTS
DE60031148T2 (en) 1999-08-31 2007-10-25 Daikin Industries, Ltd. UV-CURABLE POLYMERIC COMPOSITION

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8902092A (en) * 1988-05-06 1989-12-05 Du Pont FLUORELASTOMER COMPOSITION
US5374484A (en) * 1992-05-11 1994-12-20 Asahi Kasei Kogyo Kabushiki Kaisha Fluorine-containing elastomer composition and molded articles made therefrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9515995A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2805705A1 (en) 2013-05-23 2014-11-26 IP Gesellschaft für Management mbH Packaging with one or more administration units comprising a sodium salt of (R)-3-[6-amino-pyridin-3-yl]-2-(1-cyclohexyl-1 H-imidazol-4-yl)-propionic acid
EP3184095A1 (en) 2013-05-23 2017-06-28 IP Gesellschaft für Management mbH Administration units comprising polymorph 1 of 2-(2-methylamino-pyrimidin-4-yl]-1h-indole-5-carboxylic acid [(s)-1-carbamoyl-2-(phenyl-pyrimidin-2-yl-amino)-ethyl]-amide

Also Published As

Publication number Publication date
JPH07196878A (en) 1995-08-01
WO1995015995A1 (en) 1995-06-15

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