CA2096689C - Fluoroelastomer coating composite - Google Patents
Fluoroelastomer coating composite Download PDFInfo
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- CA2096689C CA2096689C CA002096689A CA2096689A CA2096689C CA 2096689 C CA2096689 C CA 2096689C CA 002096689 A CA002096689 A CA 002096689A CA 2096689 A CA2096689 A CA 2096689A CA 2096689 C CA2096689 C CA 2096689C
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- chloride
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- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
Abstract
A coating composition useful, for example, in the preparation of automotive gaskets and the like, the composition comprising:
(1) a fluoroelastomer;
(2) a quaternary ammonium or quaternary phosphonium salt accelerator;
(3) a polyol;
(4) an acid acceptor;
(5) an oil-soluble chelating agent; and (6) an organic solvent.
(1) a fluoroelastomer;
(2) a quaternary ammonium or quaternary phosphonium salt accelerator;
(3) a polyol;
(4) an acid acceptor;
(5) an oil-soluble chelating agent; and (6) an organic solvent.
Description
FLUOROELASTOMER COATING COMPOSITION
Field of the Inyention The present invention relates to a liquid coating composition comprising fluoroelastomer and coatings prepared therefrom.
Background In automotive gaskets., e.g., cylinder gaskets, f luoroelastomer coated metals have been used as substitutes.for the asbestos. For example, Japanese Unexamined Patent Publication (KOkai) No. 62-248453 discloses a composition containing a fluoroelastomer, a polyol, a quaternary ammonium salt accelerator or a quaternary phosphonium salt accelerator, and an acid 2 0 acceptor.
However, such a composition has a short shelf life and, accordingly, was not necessarily satisfactory, because it must be cured for a prolonged period.
on the other hand, it has been known that carboxylic 25. acid is used to form a salt or chelate with the metal ion, whereby the metal ion is inactivated in order to extend the shelf life.
However, carboxylic acids are usually hydrophilic and, thus, incompatible with the components of elastomer 30 compositions. Also, it is difficult to add the carboxylic acid to an elastomer composition.
Moreover, a relatively low molecular weight amine accelerates the curing rate when added to a fluoroelastomer composition, but at the same time, it 35 markedly shortens the shelf fife and, accordingly, it r cannot generally be employed. ' Thus, it is an object of this invention to provide a coating composition containing fluoroelastomer having a prolonged shelf life and decreased curing time.
Brief Description of the Drawina Fig. 1 is a graph that compares the viscosity change over time of a composition of the present invention containing an oil-soluble chelating agent (Example 1) with that of the a composition containing no oil-soluble l0 chelating agent (Comparative Example 1).
Summary of the Invention A liquid, coating composition comprising the following components:
(1) a fluoroelastomer;
(2) a quaternary ammonium salt or quaternary phosphonium salt accelerator;
Field of the Inyention The present invention relates to a liquid coating composition comprising fluoroelastomer and coatings prepared therefrom.
Background In automotive gaskets., e.g., cylinder gaskets, f luoroelastomer coated metals have been used as substitutes.for the asbestos. For example, Japanese Unexamined Patent Publication (KOkai) No. 62-248453 discloses a composition containing a fluoroelastomer, a polyol, a quaternary ammonium salt accelerator or a quaternary phosphonium salt accelerator, and an acid 2 0 acceptor.
However, such a composition has a short shelf life and, accordingly, was not necessarily satisfactory, because it must be cured for a prolonged period.
on the other hand, it has been known that carboxylic 25. acid is used to form a salt or chelate with the metal ion, whereby the metal ion is inactivated in order to extend the shelf life.
However, carboxylic acids are usually hydrophilic and, thus, incompatible with the components of elastomer 30 compositions. Also, it is difficult to add the carboxylic acid to an elastomer composition.
Moreover, a relatively low molecular weight amine accelerates the curing rate when added to a fluoroelastomer composition, but at the same time, it 35 markedly shortens the shelf fife and, accordingly, it r cannot generally be employed. ' Thus, it is an object of this invention to provide a coating composition containing fluoroelastomer having a prolonged shelf life and decreased curing time.
Brief Description of the Drawina Fig. 1 is a graph that compares the viscosity change over time of a composition of the present invention containing an oil-soluble chelating agent (Example 1) with that of the a composition containing no oil-soluble l0 chelating agent (Comparative Example 1).
Summary of the Invention A liquid, coating composition comprising the following components:
(1) a fluoroelastomer;
(2) a quaternary ammonium salt or quaternary phosphonium salt accelerator;
(3) a polyol;
(4) an acid acceptor;
(5) an oil-soluble chelating agent; and (6) an organic solvent.
By adding an oil-soluble chelating agent, the coating composition of the present invention is almost entirely free from any variation of viscosity of the solution during storage, and has a prolonged storage stability. With regard to the curing characteristics, it is advantageous in that the curing time can be shortened.
On the other hand, the addition of an oil-soluble chelating agent does not disadvantageously influence the dry physical properties, heat aging, or adhesion characteristics to metals.
According to one aspect of the present invention, there is provided a coating composition comprising a fluoroelastomer, and for each one hundred parts by weight of the fluoroelastomer: (1) a quaternary ammonium or quaternary phosphonium accelerator; (2) a polyol; (3) an acid acceptor;
(4) about 0.1 to 5 parts by weight of an oil-soluble chelating agent; and (5) an organic solvent.
Detailed Description of the Invention The present inventors have carried out serious studies in order to solve the above-described object. As a result, it has been discovered that the shelf life can -2a-209~~$9 be extended and th.e curing time can be shortened by adding an oil-soluble chelating agent to a fluoroelastome:r composition, whereby the present invention has been achieved.
To be specific, the present invention is to provide a coating com~~osition comprising the following components:
(1) a fluoroelastomer;
(2) a quaternary ammonium salt or quaternary phosphonium salt accelerator;
(3) a polyol;
( 4 ) an acid acceptor;
(5) an oil-soluble chelating agent; and (6) an organic solvent.
As the fluoroelastomers to be used in the present invention, conventional fluoroelastomers such as vinylidene flu.oride--hexafluoropropene copolymers, vinylidene flu.oride-hexafluoropropene-tetrafluoroethylene terpolymers, tetrafluoroethylene-propylene copolymers, and the like may be employed.
The accelerators suitable for the present invention are quaternary ammonium salt accelerators or quaternary phosphonium salt accelerators, which are used in combination with polyols as a crosslinking agent. They have the merits of being able to obtain a rapid curing rate and making the shelf life of the composition relatively long.
As the polyols used in combination with the accelerators, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 2,2-bis(4-hydroxyphenyl)perfluoropropane [bisphenol AF], hydroquinone, catechol, resorcin, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenylsulfone, 2,2-bis(4-hydroxyphenyl)butane, and the like are used, with bisphenol A, bisphenol AF and hydroquinone being preferably used. They may be also in the form of their alkali metal salts ar alkaline earth metal salts.
~o~ oo~~
As useful quaternary ammonium salts are compounds represented by the following formula (I):
R12 ~+
Ri N R X' (n R
wherein: R1 i.o R~ are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alken~,~l groups, polyoxyalkylene groups and fluoroalkyl groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates.
Examples of such compounds (I) include tetraphenylamrnonium chloride, tetraphenylammonium bromide, tetraoctylammonium chloride, tetra-n-butylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, triphenylbenzylammonium chloride, triphenylbenz~~lammonium bromide, triphenylbenzylammonium stearate, triphenylbenzylammonium benzoate, triphenylisobutylammonium bromide, trioctyl-n-butylammonium chloride, trioctylbenzylammonium chloride, trioctylbenzyl.ammonium acetate, triphenyl-2,4-dichlorobenzyl.ammonium chloride, trioctylmetho~s:yeth.oxyethylammonium chloride, triphenyletho~c:ycarbonylmethylammonium chloride, triphenylallylammonium chloride, 1-alkyl pyridium salt, 5-aralkyl-1,5-diazabicyclo[4.3.0]-5-nonenium salt, 8-aralkyl-1,8-diazabicyclo[5.4.0]-7-undecenium salt, and the like.
As useful quaternary phosphonium salts are compounds represented by the following formula (II):
R
2 +
R P R X-R
wherein: Rl to R4 are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alkenyl groups, polyoxyalkylene groups, and fluoroalkyl~groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates, and the like.
Examples of such compounds include tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraoctylphosphonium chloride, tetra-n-butylphosphonium chloride, tetraethylphosphonium chloride, tetramethylphosphonium chloride, tetramethylphosphonium bromide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, triphenylbenzylphosphonium stearate, triphenylbenzylphosphonium benzoate, triphenylisobutylphosphonium bromide, trioctyl-n-butylphosphonium chloride, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium acetate, triphenyl-2,4-dichlorobenzylphosphonium chloride, trioctylmethoxyethylphosphonium chloride, triphenylethoxycarbonylmethylphosphonium chloride, triphenylallylphosphonium chloride, and the like.
Organic solvents useful in the fluoroelastomer coating composition include ketone, alcohol and ester solvents. Suitable organic solvents include methyl isobutyl ketone, methanol, ethanol, isopropanol, ethyl acetate, cellosolve acetate and sorbitol acetate. The organic solvents can be used singly or as a mixture of two or more. However, if a mixture of ketone and alcohol solvents is employed, and the ratio of ketone in the mixture is high, gelation is accelerated and stability improves with time elapsed. If the ratio of alcohol in the mixture is high, the solubility is decreased. The weight ratio of about 90 to 30% of the ketone to about 10 to 70% of the alcohol is preferred as the mixed ratio.
The "oil-soluble chelating agents" used in the present invention are soluble in organic solvents, such as ketones, alcohols or ester solvents which solvents are generally known as solvents for dissolving fluoroelastomers, and chelate metal ions (e.g., Ca2+~
Mg2+, etc.). In general, known chelating agents, for example, ethylene diamine tetraacetic acid (EDTA), are soluble in water but insoluble in organic solvents.
Accordingly, they have poor compatibility with the ketone, alcohol, or ester solvents which are used as the organic solvent in this invention. Furthermore, even if one of the water-soluble chelating agents is singly used in the kneading of the fluoroelastomer, no uniform compound can be obtained due to its poor compatibility.
However, such water-soluble chelating agents can be made useful in this invention by increasing their lipophilicity by reacting part of the carboxyl groups on the chelating agent with an amine to form an amine salt.
Thus, preferred oil-soluble chelating agent are partial alkylamine salts of polybasic carboxylic acids, and they can be prepared by reacting known chelating agents, such as triethylenetetraamine hexaacetic acid (TTHA), ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA), glycol ether diamine tetraacetic acid (GEDTA), and the like, with amines, such as lower alkyl amines (e. g., methyl amine, ethyl amine, n-propyl amine, isopropyl amine, n-butyl °amine, and isobutyl amine). Butylamine salts of DTPA, represented by the following formula, are particularly preferable .
HOCOCH ~ ~CH CpONH R
2 NCH2CH2NCH2CH2N~
/ I
1o HOCOCH2 CH2COOH ~2COONH3 R
R: Butyl Because the oil-soluble chelating agents are soluble in organic solvents, their compatibility with the ketone, alcohol, and ester solvents which are used as the organic solvents in the fluoroelastomer coating composition are improved, and simultaneously, their compatibility with the fluoroelastomer during the kneading can also be solved. Specifically, when the oil-soluble chelating agent is used, it is easily dispersed in the coating composition to chelate metal ions effectively, thereby contributing to the stabilization of the shelf life of the fluoroelastomer coating composition.
Although the oil-soluble chelating agent contains at least one amine group, it is blocked by the carboxyl group, so the elastomer components of the composition are stable in the solution. Moreover, since the salt will decompose during the curing of the elastomer components (160-200°C), a rapid curing rate of~the coating can be obtained.
In the fluoroelastomer coating composition, the polyol in the ratio of about 0.1 to l0 parts, preferably about 0.5 to 6 parts by weight, the quaternary salt accelerator in the ratio of about 0.5 to 10 parts by weight, preferably about 1 to 8 parts by weight, and magnesium oxide in the ratio of about 1 to 30 parts by ~~~~~89 weight, preferably about 5 to 15 parts by weight, are used respectively, based on 100 parts by weight of the fluoroelastoms:r. Also, the oil-soluble chelating agent is added in an amaunt of 0.1 to 5, preferably 0.5 to 3, parts by weight based on 100 parts by weight of the fluoroelastomer. The addition of too large amount of the oil-soluble chelating agent adversely influences the adhering properties with the metal, etc. Conversely, if it is added in too small an amount, the effect of the present invention cannot be obtained. Components (1) through (5) of the fluoroelastomer coating composition are present in the composition at a level of 10 to 40 weight percent:. The coating composition is a solution or suspension of components (1) through (5) in the organic solvent.
The production of the fluoroelastomer composition can be carried out. by incorporating the respective components in the organic solvent, and thoroughly kneading the whole system. The oil-soluble chelating agent may be either incorporated together with the other components, or added after the other components.
The fluoroelastomer coating composition thus prepared can k>e used as a fluoroelastomer coating material for coating a metal surface, etc. When coating, this solution is applied on a metal plate treated with a commercially available silicon primer, etc., dried, and adhesion by curing .is carried out by heating it in an oven.
Examples The present invention will now be described in greater detail with reference to the working examples.
Examples .L and 2 and Comparative Examples 1 and 2 In order to prepare an octyl amine salt of DTPA, 20 m2 of methanol, 1_hen 10 g of DTPA and 5.74 g of n--g_ octyl amine were added to a~100 mP volume beaker. The mixture was stirred with a magnetic stirrer overnight to obtain a pale yellow liquid.
Examples 1 and 2 and comparative Examples 1 and 2 were prepared by kneading the ingredients set forth in Table 1 in the usual rolls. In Table 1, the amount of each component is given as parts by weight per 100 parts by weight of the fluoroelastomer.
The kneaded mixtures were then dissolved in a mixture of methyl isobutyl ketone-methanol (mixed ratio:
90 . 10) so as to be 30% by weight solid concentration.
The liquid fluoroelastomer compositions were then applied to stainless steel plates (SUS 301) treated with a primer containing a silane coupling agent, dried at 120°C for 30 minutes, and then cured at 200°C for 4 hours.
The physical properties and heat aging of the resulting fluoroelastomer coating compositions are given in Table 1.
The cure theology characteristics were measured at 170°C using a Monsanto ODR Model 2000 rheometer.
The measurements of cure theology characteristics, physical properties and heat aging characteristics were conducted in accordance with JIS K6301.
The adhesion characteristics of the cured coating composition to the metal sheet were measured by cross-cut and pencil hardness tests (both in accordance with JIS
K54000). The results of the tests are given in Table 2.
The space on carrying out the square test was 1.0 mm.
The stability of the fluoroelastomer coating composition was evaluated by measuring the time for the composition to gel at room temperature. The results of the stability tests are given in Table 3.
The viscosity change of the composition of Example 1 and Comparative Example 1 as a function of time was measured. The results are depicted in Figure 1.
_g_ ' 76950-6 T le Ex. 1 Ex. Comp. Ex. Comb. Ex.
Fluoroelastomert 100 100 100 100 TPBCI2 0.51 0.51 0.51 0.51 Bisphenol AF 1.91 1.91 1.91 1.91 MT carbon black 30 30 30 30 Magnesium Oxide3 10 10 10 10 Calcium Hydroxide4 1 1 Octyl amine salt 1 1 of DTPA
Cure rheologv Co'~ 170C
Time (min.) 24 12 24 12 Minimum torque (in-lb) 8 8 9 10 Maximum torque (in-Ib) 94 87 63 54 t' 90 (min.) 12.4 7.9 15.4 9.6 Physical properties Press cure time (min.) 15 10 24 12 2 ~ 170C
Post cure, 24 hrs.
Tensile (kg~/cm2) 157 154 148 141 100 ~ Modules 56 56 260 290 2 (kg~/cm2) Elongation (30) 230 210 44 44 Hardness 80 80 77 77 Heat aging. 70 hrs.
Cc~
Tensile change (9b) -10 -9 -3 -5 Elongation change (9b) -14 0 +6 -S
Harness points change +2 +2 +2 +3 1FLUORELTM fluoroelastomer 35 2Tribenzylphosphonium chloride TM
3Kyowa Mg0 #30 TM
4RENOFITE, available commerci ally from Rhein Chemical, Germany Table 2 Ex.l Ex. l' Ex. 2 Comp. Comp.
Ex. 1 Ex. 2 Pencil Hardness Test H H H H H
(Pencil Hardness) Cross-cut Test 10 10 10 10 10 (points) In Example 1', the sample of Example 1 was stored for 3 months, and the test was then conducted.
T$ble 3 Ex. 1 Ex. 2 Comp. Comp.
Ex. 1 Ex. 2 Time to Not gelled More than 15 days 4 days gelation after more one month than 3 months
By adding an oil-soluble chelating agent, the coating composition of the present invention is almost entirely free from any variation of viscosity of the solution during storage, and has a prolonged storage stability. With regard to the curing characteristics, it is advantageous in that the curing time can be shortened.
On the other hand, the addition of an oil-soluble chelating agent does not disadvantageously influence the dry physical properties, heat aging, or adhesion characteristics to metals.
According to one aspect of the present invention, there is provided a coating composition comprising a fluoroelastomer, and for each one hundred parts by weight of the fluoroelastomer: (1) a quaternary ammonium or quaternary phosphonium accelerator; (2) a polyol; (3) an acid acceptor;
(4) about 0.1 to 5 parts by weight of an oil-soluble chelating agent; and (5) an organic solvent.
Detailed Description of the Invention The present inventors have carried out serious studies in order to solve the above-described object. As a result, it has been discovered that the shelf life can -2a-209~~$9 be extended and th.e curing time can be shortened by adding an oil-soluble chelating agent to a fluoroelastome:r composition, whereby the present invention has been achieved.
To be specific, the present invention is to provide a coating com~~osition comprising the following components:
(1) a fluoroelastomer;
(2) a quaternary ammonium salt or quaternary phosphonium salt accelerator;
(3) a polyol;
( 4 ) an acid acceptor;
(5) an oil-soluble chelating agent; and (6) an organic solvent.
As the fluoroelastomers to be used in the present invention, conventional fluoroelastomers such as vinylidene flu.oride--hexafluoropropene copolymers, vinylidene flu.oride-hexafluoropropene-tetrafluoroethylene terpolymers, tetrafluoroethylene-propylene copolymers, and the like may be employed.
The accelerators suitable for the present invention are quaternary ammonium salt accelerators or quaternary phosphonium salt accelerators, which are used in combination with polyols as a crosslinking agent. They have the merits of being able to obtain a rapid curing rate and making the shelf life of the composition relatively long.
As the polyols used in combination with the accelerators, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 2,2-bis(4-hydroxyphenyl)perfluoropropane [bisphenol AF], hydroquinone, catechol, resorcin, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenylsulfone, 2,2-bis(4-hydroxyphenyl)butane, and the like are used, with bisphenol A, bisphenol AF and hydroquinone being preferably used. They may be also in the form of their alkali metal salts ar alkaline earth metal salts.
~o~ oo~~
As useful quaternary ammonium salts are compounds represented by the following formula (I):
R12 ~+
Ri N R X' (n R
wherein: R1 i.o R~ are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alken~,~l groups, polyoxyalkylene groups and fluoroalkyl groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates.
Examples of such compounds (I) include tetraphenylamrnonium chloride, tetraphenylammonium bromide, tetraoctylammonium chloride, tetra-n-butylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, triphenylbenzylammonium chloride, triphenylbenz~~lammonium bromide, triphenylbenzylammonium stearate, triphenylbenzylammonium benzoate, triphenylisobutylammonium bromide, trioctyl-n-butylammonium chloride, trioctylbenzylammonium chloride, trioctylbenzyl.ammonium acetate, triphenyl-2,4-dichlorobenzyl.ammonium chloride, trioctylmetho~s:yeth.oxyethylammonium chloride, triphenyletho~c:ycarbonylmethylammonium chloride, triphenylallylammonium chloride, 1-alkyl pyridium salt, 5-aralkyl-1,5-diazabicyclo[4.3.0]-5-nonenium salt, 8-aralkyl-1,8-diazabicyclo[5.4.0]-7-undecenium salt, and the like.
As useful quaternary phosphonium salts are compounds represented by the following formula (II):
R
2 +
R P R X-R
wherein: Rl to R4 are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alkenyl groups, polyoxyalkylene groups, and fluoroalkyl~groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates, and the like.
Examples of such compounds include tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraoctylphosphonium chloride, tetra-n-butylphosphonium chloride, tetraethylphosphonium chloride, tetramethylphosphonium chloride, tetramethylphosphonium bromide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, triphenylbenzylphosphonium stearate, triphenylbenzylphosphonium benzoate, triphenylisobutylphosphonium bromide, trioctyl-n-butylphosphonium chloride, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium acetate, triphenyl-2,4-dichlorobenzylphosphonium chloride, trioctylmethoxyethylphosphonium chloride, triphenylethoxycarbonylmethylphosphonium chloride, triphenylallylphosphonium chloride, and the like.
Organic solvents useful in the fluoroelastomer coating composition include ketone, alcohol and ester solvents. Suitable organic solvents include methyl isobutyl ketone, methanol, ethanol, isopropanol, ethyl acetate, cellosolve acetate and sorbitol acetate. The organic solvents can be used singly or as a mixture of two or more. However, if a mixture of ketone and alcohol solvents is employed, and the ratio of ketone in the mixture is high, gelation is accelerated and stability improves with time elapsed. If the ratio of alcohol in the mixture is high, the solubility is decreased. The weight ratio of about 90 to 30% of the ketone to about 10 to 70% of the alcohol is preferred as the mixed ratio.
The "oil-soluble chelating agents" used in the present invention are soluble in organic solvents, such as ketones, alcohols or ester solvents which solvents are generally known as solvents for dissolving fluoroelastomers, and chelate metal ions (e.g., Ca2+~
Mg2+, etc.). In general, known chelating agents, for example, ethylene diamine tetraacetic acid (EDTA), are soluble in water but insoluble in organic solvents.
Accordingly, they have poor compatibility with the ketone, alcohol, or ester solvents which are used as the organic solvent in this invention. Furthermore, even if one of the water-soluble chelating agents is singly used in the kneading of the fluoroelastomer, no uniform compound can be obtained due to its poor compatibility.
However, such water-soluble chelating agents can be made useful in this invention by increasing their lipophilicity by reacting part of the carboxyl groups on the chelating agent with an amine to form an amine salt.
Thus, preferred oil-soluble chelating agent are partial alkylamine salts of polybasic carboxylic acids, and they can be prepared by reacting known chelating agents, such as triethylenetetraamine hexaacetic acid (TTHA), ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA), glycol ether diamine tetraacetic acid (GEDTA), and the like, with amines, such as lower alkyl amines (e. g., methyl amine, ethyl amine, n-propyl amine, isopropyl amine, n-butyl °amine, and isobutyl amine). Butylamine salts of DTPA, represented by the following formula, are particularly preferable .
HOCOCH ~ ~CH CpONH R
2 NCH2CH2NCH2CH2N~
/ I
1o HOCOCH2 CH2COOH ~2COONH3 R
R: Butyl Because the oil-soluble chelating agents are soluble in organic solvents, their compatibility with the ketone, alcohol, and ester solvents which are used as the organic solvents in the fluoroelastomer coating composition are improved, and simultaneously, their compatibility with the fluoroelastomer during the kneading can also be solved. Specifically, when the oil-soluble chelating agent is used, it is easily dispersed in the coating composition to chelate metal ions effectively, thereby contributing to the stabilization of the shelf life of the fluoroelastomer coating composition.
Although the oil-soluble chelating agent contains at least one amine group, it is blocked by the carboxyl group, so the elastomer components of the composition are stable in the solution. Moreover, since the salt will decompose during the curing of the elastomer components (160-200°C), a rapid curing rate of~the coating can be obtained.
In the fluoroelastomer coating composition, the polyol in the ratio of about 0.1 to l0 parts, preferably about 0.5 to 6 parts by weight, the quaternary salt accelerator in the ratio of about 0.5 to 10 parts by weight, preferably about 1 to 8 parts by weight, and magnesium oxide in the ratio of about 1 to 30 parts by ~~~~~89 weight, preferably about 5 to 15 parts by weight, are used respectively, based on 100 parts by weight of the fluoroelastoms:r. Also, the oil-soluble chelating agent is added in an amaunt of 0.1 to 5, preferably 0.5 to 3, parts by weight based on 100 parts by weight of the fluoroelastomer. The addition of too large amount of the oil-soluble chelating agent adversely influences the adhering properties with the metal, etc. Conversely, if it is added in too small an amount, the effect of the present invention cannot be obtained. Components (1) through (5) of the fluoroelastomer coating composition are present in the composition at a level of 10 to 40 weight percent:. The coating composition is a solution or suspension of components (1) through (5) in the organic solvent.
The production of the fluoroelastomer composition can be carried out. by incorporating the respective components in the organic solvent, and thoroughly kneading the whole system. The oil-soluble chelating agent may be either incorporated together with the other components, or added after the other components.
The fluoroelastomer coating composition thus prepared can k>e used as a fluoroelastomer coating material for coating a metal surface, etc. When coating, this solution is applied on a metal plate treated with a commercially available silicon primer, etc., dried, and adhesion by curing .is carried out by heating it in an oven.
Examples The present invention will now be described in greater detail with reference to the working examples.
Examples .L and 2 and Comparative Examples 1 and 2 In order to prepare an octyl amine salt of DTPA, 20 m2 of methanol, 1_hen 10 g of DTPA and 5.74 g of n--g_ octyl amine were added to a~100 mP volume beaker. The mixture was stirred with a magnetic stirrer overnight to obtain a pale yellow liquid.
Examples 1 and 2 and comparative Examples 1 and 2 were prepared by kneading the ingredients set forth in Table 1 in the usual rolls. In Table 1, the amount of each component is given as parts by weight per 100 parts by weight of the fluoroelastomer.
The kneaded mixtures were then dissolved in a mixture of methyl isobutyl ketone-methanol (mixed ratio:
90 . 10) so as to be 30% by weight solid concentration.
The liquid fluoroelastomer compositions were then applied to stainless steel plates (SUS 301) treated with a primer containing a silane coupling agent, dried at 120°C for 30 minutes, and then cured at 200°C for 4 hours.
The physical properties and heat aging of the resulting fluoroelastomer coating compositions are given in Table 1.
The cure theology characteristics were measured at 170°C using a Monsanto ODR Model 2000 rheometer.
The measurements of cure theology characteristics, physical properties and heat aging characteristics were conducted in accordance with JIS K6301.
The adhesion characteristics of the cured coating composition to the metal sheet were measured by cross-cut and pencil hardness tests (both in accordance with JIS
K54000). The results of the tests are given in Table 2.
The space on carrying out the square test was 1.0 mm.
The stability of the fluoroelastomer coating composition was evaluated by measuring the time for the composition to gel at room temperature. The results of the stability tests are given in Table 3.
The viscosity change of the composition of Example 1 and Comparative Example 1 as a function of time was measured. The results are depicted in Figure 1.
_g_ ' 76950-6 T le Ex. 1 Ex. Comp. Ex. Comb. Ex.
Fluoroelastomert 100 100 100 100 TPBCI2 0.51 0.51 0.51 0.51 Bisphenol AF 1.91 1.91 1.91 1.91 MT carbon black 30 30 30 30 Magnesium Oxide3 10 10 10 10 Calcium Hydroxide4 1 1 Octyl amine salt 1 1 of DTPA
Cure rheologv Co'~ 170C
Time (min.) 24 12 24 12 Minimum torque (in-lb) 8 8 9 10 Maximum torque (in-Ib) 94 87 63 54 t' 90 (min.) 12.4 7.9 15.4 9.6 Physical properties Press cure time (min.) 15 10 24 12 2 ~ 170C
Post cure, 24 hrs.
Tensile (kg~/cm2) 157 154 148 141 100 ~ Modules 56 56 260 290 2 (kg~/cm2) Elongation (30) 230 210 44 44 Hardness 80 80 77 77 Heat aging. 70 hrs.
Cc~
Tensile change (9b) -10 -9 -3 -5 Elongation change (9b) -14 0 +6 -S
Harness points change +2 +2 +2 +3 1FLUORELTM fluoroelastomer 35 2Tribenzylphosphonium chloride TM
3Kyowa Mg0 #30 TM
4RENOFITE, available commerci ally from Rhein Chemical, Germany Table 2 Ex.l Ex. l' Ex. 2 Comp. Comp.
Ex. 1 Ex. 2 Pencil Hardness Test H H H H H
(Pencil Hardness) Cross-cut Test 10 10 10 10 10 (points) In Example 1', the sample of Example 1 was stored for 3 months, and the test was then conducted.
T$ble 3 Ex. 1 Ex. 2 Comp. Comp.
Ex. 1 Ex. 2 Time to Not gelled More than 15 days 4 days gelation after more one month than 3 months
Claims (11)
1. A coating composition comprising a fluoroelastomer, and for each one hundred parts by weight of the fluoroelastomer:
(1) a quaternary ammonium or quaternary phosphonium accelerator;
(2) a polyol;
(3) an acid acceptor;
(4) about 0.1 to 5 parts by weight of an oil-soluble chelating agent; and (5) an organic solvent.
(1) a quaternary ammonium or quaternary phosphonium accelerator;
(2) a polyol;
(3) an acid acceptor;
(4) about 0.1 to 5 parts by weight of an oil-soluble chelating agent; and (5) an organic solvent.
2. A composition according to claim 1, wherein said fluoroelastomer is a vinylidene fluoride-hexafluoropropene copolymer, a vinylidene fluoridehexafluoropropene-tetrafluoroethylene terpolymer, or a tetrafluoroethylene-propylene copolymer.
3. A composition according to claim 1 or 2, wherein the polyol is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)perfluoropropane, hydroquinone, catechol, resorcin, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenylsulfone, and 2,2-bis(4-hydroxyphenyl)butane.
4. A composition according to any one of claims 1 to 3, wherein the quaternary ammonium accelerator salt is a compound represented by the following formula:
wherein;
R1 to R4 are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alkenyl groups, polyoxyalkylene groups and fluoroalkyl groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates.
wherein;
R1 to R4 are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alkenyl groups, polyoxyalkylene groups and fluoroalkyl groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates.
5. A composition according to claim 4, wherein the quaternary ammonium accelerator is selected from the group consisting of tetraphenylammonium chloride, tetraphenylammonium bromide, tetraoctylammonium chloride, tetra-n-butylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, triphenylbenzylammonium chloride, triphenylbenzylammonium bromide, triphenylbenzylammonium stearate, triphenylbenzylammonium benzoate, triphenylisobutylammonium bromide, trioctyl-n-butylammonium chloride, trioctylbenzylammonium chloride, trioctylbenzylammonium acetate, triphenyl-2,4-dichlorobenzylammonium chloride, trioctylmethoxyethoxyethylammonium chloride, triphenylethoxycarbonylmethylammonium chloride, triphenylallylammonium chloride, 1-alkyl pyridium salt, 5-aralkyl-1,5-diazabicyclo[4.3.0]-5-nonenium salt, and 8-aralkyl-1,8-diazabicyclo[5.4.0]-7-undecenium salt.
6. A composition according to any one of claims 1 to 4, said quaternary phosphonium accelerator salt is a compound represented by the following formula:
wherein:
R1 to R4 are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alkenyl groups, polyoxyalkylene groups, and fluoroalkyl groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates.
wherein:
R1 to R4 are independently selected from the group consisting of alkyl groups, aryl groups, aralkyl groups, alkenyl groups, polyoxyalkylene groups, and fluoroalkyl groups; and X- is an anion selected from the group consisting of halides, hydroxylates, alkoxylates, carboxylates, phenoxides, sulfonates, sulfates, sulfites, carbonates, and nitrates.
7. A composition according to claim 6, wherein said phosphonium chloride accelerator salt is selected from the group consisting of tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraoctylphosphonium chloride, tetra-n-butylphosphonium chloride, tetraethylphosphonium chloride, tetramethylphosphonium chloride, tetramethylphosphonium bromide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, triphenylbenzylphosphonium stearate, triphenylbenzylphosphonium benzoate, triphenylisobutylphosphonium bromide, trioctyl-n-butylphosphonium chloride, trioctylbenzylphosphonium chloride, trioctylbenzylphosphonium acetate, triphenyl-2,4-dichlorobenzylphosphonium chloride, trioctylmethoxyethoxyethylphosphonium chloride, triphenylethoxycarbonylmethylphosphonium chloride, and triphenylallylphosphonium chloride.
8. A composition according to any one of claims 1 to 7, wherein the oil-soluble chelating agent is a partial alkylamine salt of a polybasic carboxylic acid, the polybasic carboxylic acid being selected from the group consisting of ethylenediamine tetraacetic acid, glycol ether diamine tetraacetic acid, and diethylenetriamine pentaacetic acid.
9. A composition according to any one of claims 1 to 8, wherein the composition comprises 10 to 40 weight percent of components (1) through (4), and 90 to 60 weight percent of component (5).
10. A composition according to claim 9, wherein components (1) through (3) are used in the following weight ratios:
(1) 0.5 to 10 parts by weight of quaternary ammonium or quaternary phosphonium salt accelerator;
(2) 0.1 to 10 parts by weight of polyol; and (3) 1 to 30 parts by weight of acid acceptor.
(1) 0.5 to 10 parts by weight of quaternary ammonium or quaternary phosphonium salt accelerator;
(2) 0.1 to 10 parts by weight of polyol; and (3) 1 to 30 parts by weight of acid acceptor.
11. A composition according to any one of claims 1 to 10, wherein the organic solvent is a ketone, ester, alcohol or mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4151710A JPH05339536A (en) | 1992-06-11 | 1992-06-11 | Fluorinated rubber composition for coating |
| JP151710/92 | 1992-06-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2096689A1 CA2096689A1 (en) | 1993-12-12 |
| CA2096689C true CA2096689C (en) | 2004-11-30 |
Family
ID=15524584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002096689A Expired - Fee Related CA2096689C (en) | 1992-06-11 | 1993-05-20 | Fluoroelastomer coating composite |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US5451625A (en) |
| EP (1) | EP0574319B1 (en) |
| JP (1) | JPH05339536A (en) |
| KR (1) | KR940005767A (en) |
| CA (1) | CA2096689C (en) |
| DE (1) | DE69316452T2 (en) |
| ES (1) | ES2111723T3 (en) |
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| US5591804A (en) * | 1995-12-21 | 1997-01-07 | Minnesota Mining And Manufacturing Company | Fluorinated onium salts, curable compositions containing same, and method of curing using same |
| US6252006B1 (en) | 1996-08-23 | 2001-06-26 | Daikin Industries Ltd. | Fluororubber coating composition |
| US6239223B1 (en) | 1997-09-05 | 2001-05-29 | Chemfab Corporation | Fluoropolymeric composition |
| US6294604B1 (en) * | 1998-03-06 | 2001-09-25 | Dyneon Llc | Polymer processing additive having improved stability |
| JP2001247572A (en) * | 2000-03-06 | 2001-09-11 | Central Glass Co Ltd | Pyrimidine derivative salt |
| JP2001316611A (en) * | 2000-05-11 | 2001-11-16 | Daikin Ind Ltd | Fluororubber coating composition |
| US6890995B2 (en) * | 2001-01-31 | 2005-05-10 | 3M Innovative Properties Company | Fluoropolymer compositions |
| US6844388B2 (en) | 2001-04-12 | 2005-01-18 | 3M Innovative Properties Company | Fluoropolymer compositions containing a nitrogen cure site monomer |
| US6794457B2 (en) | 2001-04-30 | 2004-09-21 | 3M Innovative Properties Company | Fluoropolymer curing system containing a nitrogen cure site monomer |
| US6685793B2 (en) | 2001-05-21 | 2004-02-03 | 3M Innovative Properties Company | Fluoropolymer bonding composition and method |
| US20050208308A1 (en) * | 2001-05-21 | 2005-09-22 | 3M Innovative Properties Company | Bonding compositions |
| US7485371B2 (en) * | 2004-04-16 | 2009-02-03 | 3M Innovative Properties Company | Bonding compositions |
| US6753087B2 (en) | 2001-05-21 | 2004-06-22 | 3M Innovative Properties Company | Fluoropolymer bonding |
| US6630047B2 (en) * | 2001-05-21 | 2003-10-07 | 3M Innovative Properties Company | Fluoropolymer bonding composition and method |
| JP5010073B2 (en) * | 2001-07-18 | 2012-08-29 | 電気化学工業株式会社 | Chloroprene-based rubber composition |
| US6773755B2 (en) * | 2001-08-08 | 2004-08-10 | 3M Innovative Properties Company | Process for preparing a multi-layer article having a fluoroplastic layer and an elastomer layer |
| US7291369B2 (en) | 2001-10-03 | 2007-11-06 | 3M Innovative Properties Company | Multi-layer articles including a fluoroelastomer layer and a barrier layer and method of making the same |
| US6844030B2 (en) | 2001-12-14 | 2005-01-18 | 3M Innovative Properties Company | Process for modifying a polymeric surface |
| US6752894B2 (en) | 2001-12-14 | 2004-06-22 | 3M Innovative Properties Company | Process for modifying a polymeric surface |
| ITMI20020598A1 (en) * | 2002-03-22 | 2003-09-22 | Ausimont Spa | VULCANIZABLE FLUOROELASTOMERS |
| US7569275B2 (en) | 2002-04-18 | 2009-08-04 | 3M Innovative Properties Company | Fluoropolymer articles |
| US20030198770A1 (en) * | 2002-04-18 | 2003-10-23 | 3M Innovative Properties Company | Composite fluoropolymer-perfluoropolymer assembly |
| US6759129B2 (en) | 2002-04-18 | 2004-07-06 | 3M Innovative Properties Company | Adhesion and bonding of multi-layer articles including a fluoropolymer layer |
| US6849314B2 (en) | 2002-04-18 | 2005-02-01 | 3M Innovative Properties Company | Fluoropolymer blends and multilayer articles |
| US20040126708A1 (en) * | 2002-12-31 | 2004-07-01 | 3M Innovative Properties Company | Method for modifying the surface of a polymeric substrate |
| US6956085B2 (en) * | 2003-02-14 | 2005-10-18 | 3M Innovative Properties Company | Fluoroelastomer compositions |
| US6986947B2 (en) * | 2003-10-09 | 2006-01-17 | 3M Innovative Properties Company | Method of modifying a fluoropolymer and articles thereby |
| US6911512B2 (en) | 2003-10-10 | 2005-06-28 | 3M Innovative Properties Company | Powder coating fluoropolymer compositions with aromatic materials |
| US7273531B2 (en) * | 2003-11-05 | 2007-09-25 | 3M Innovative Properties Company | Method of modifying a fluoropolymeric substrate and composite articles thereby |
| RU2006123335A (en) * | 2003-12-30 | 2008-02-10 | ЗМ Инновейтив Пропертиз Компани (US) | METHOD FOR COAGULATION OF FLUOROPOLYMERS AND COMPOSITIONS |
| US7344796B2 (en) * | 2004-02-18 | 2008-03-18 | Freudenberg-Nok General Partnership | Fluoroelastomer gasket compositions |
| US20050187331A1 (en) * | 2004-02-20 | 2005-08-25 | Yuan Hui L. | Fluoroelastomer gasket compositions |
| US20050187325A1 (en) * | 2004-02-20 | 2005-08-25 | Yuan Hui L. | Silicone gasket compositions |
| JP4578122B2 (en) * | 2004-03-05 | 2010-11-10 | 中部キレスト株式会社 | Production method of lipophilic chelating agent |
| ITMI20040830A1 (en) | 2004-04-27 | 2004-07-27 | Solvay Solexis Spa | VULCANIZABLE FLUOROELASTOMERS |
| US20060025504A1 (en) * | 2004-07-29 | 2006-02-02 | Oriani Steven R | Process aid for melt processable polymers that contain hindered amine light stabilizer |
| US7402630B2 (en) * | 2004-12-16 | 2008-07-22 | 3M Innovative Properties Company | Curing compositions for fluoropolymers |
| KR100663357B1 (en) * | 2005-02-22 | 2007-01-02 | 삼성전자주식회사 | Methods of forming a transistor having a metal nitride layer pattern |
| US7294677B2 (en) * | 2005-08-25 | 2007-11-13 | 3M Innovative Properties Company | Catalyst for making fluoroelastomer compositions and methods of using the same |
| JP5176267B2 (en) * | 2005-08-31 | 2013-04-03 | 日本ゼオン株式会社 | Nitrile rubber composition and cross-linked product |
| EP2115058A1 (en) * | 2007-01-03 | 2009-11-11 | Solvay Solexis, Inc. | Fluoroelastomer composition |
| TW200920877A (en) * | 2007-11-05 | 2009-05-16 | Magtech Technology Co Ltd | Method for soldering magnesium alloy workpieces |
| EP2445939B1 (en) | 2009-06-25 | 2020-09-23 | 3M Innovative Properties Company | Curing compositions for fluoropolymers |
| US8580886B2 (en) | 2011-09-20 | 2013-11-12 | Dow Corning Corporation | Method for the preparation and use of bis (alkoxysilylorgano)-dicarboxylates |
| EP2760957B1 (en) * | 2011-09-29 | 2016-02-24 | 3M Innovative Properties Company | Catalyzing amino-substituted organosilane ester primers |
| CN104024265B (en) | 2011-12-02 | 2017-03-01 | 道康宁公司 | Ester functional silane and its preparation and use；And group with imine moiety is as the purposes of phase transfer catalyst |
| EP3456751A1 (en) * | 2017-09-15 | 2019-03-20 | Solvay Specialty Polymers Italy S.p.A. | Method for coating a substrate using fluorinated block copolymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| NL6912561A (en) * | 1968-08-19 | 1970-02-23 | ||
| JPS604552A (en) * | 1983-06-23 | 1985-01-11 | Mitsubishi Gas Chem Co Inc | Electrically conductive composition |
| JPS62248459A (en) * | 1986-04-23 | 1987-10-29 | Shiraishi Calcium Kk | Pellet-like mineral mixed feed |
| US5041476A (en) * | 1988-04-05 | 1991-08-20 | Phillips Petroleum Company | Rapidly crystallizing polyethylene terephthalate blends |
| JP2730154B2 (en) * | 1989-03-22 | 1998-03-25 | エヌオーケー株式会社 | Fluoro rubber compound solution |
| US5089173A (en) * | 1990-05-02 | 1992-02-18 | Advanced Products Inc. | Highly conductive polymer thick film compositions |
-
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- 1992-06-11 JP JP4151710A patent/JPH05339536A/en active Pending
-
1993
- 1993-05-20 CA CA002096689A patent/CA2096689C/en not_active Expired - Fee Related
- 1993-05-31 KR KR1019930009699A patent/KR940005767A/en not_active Application Discontinuation
- 1993-06-09 US US08/073,896 patent/US5451625A/en not_active Expired - Lifetime
- 1993-06-10 EP EP93401484A patent/EP0574319B1/en not_active Expired - Lifetime
- 1993-06-10 DE DE69316452T patent/DE69316452T2/en not_active Expired - Fee Related
- 1993-06-10 ES ES93401484T patent/ES2111723T3/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0574319A1 (en) | 1993-12-15 |
| DE69316452T2 (en) | 1998-09-17 |
| KR940005767A (en) | 1994-03-22 |
| US5658671A (en) | 1997-08-19 |
| US5451625A (en) | 1995-09-19 |
| ES2111723T3 (en) | 1998-03-16 |
| JPH05339536A (en) | 1993-12-21 |
| DE69316452D1 (en) | 1998-02-26 |
| EP0574319B1 (en) | 1998-01-21 |
| CA2096689A1 (en) | 1993-12-12 |
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