Patent Application
20160002377
1. Technical Field
The present invention relates generally to mold releasing agent, and more particularly to a type of mold releasing agent which belongs to fluorine-containing copolymer.
2. Description of Related Art
Moldings made of resin or rubber are produced by filling the materials into a mold, wherein the mold is typically coated with mold releasing agent in order to get moldings out of the mold easier. Since the mold releasing agent is applied repeatedly, there would be an accumulation on the mold when the frequency of use increases. As a result, the fineness of the moldings would be affected, and it would even pollute the environment.
The conventional mold releasing agent is a kind of fluoride which is mainly chemical compounds of perfluoroalkyl chains with eight or more carbon atoms. However, according to recent studies, long-chain perfluoroalkyl compounds may be degraded to perfluorocaprylic acid (PFOA) in certain conditions, and PFOA tends to accumulate in vivo. Therefore, the conventional kind of fluoride is gradually replaced by that of short-chain perfluoroalkyl, which has lower environmental persistence.
In view of the above, the primary objective of the present invention is to provide a mold releasing agent, which has comparable releasing performance and longevity to long-chain copolymers containing halothane.
The mold releasing agent provided in the present invention includes a fluorine-containing monomer, an acrylic ester monomer, and an acid monomer.
In an embodiment, the fluorine-containing monomer is represented by the general expression CH2═C(—X)C(═O)—Y—Z—Rf, where X is hydrogen atom, monovalent organic group, halogen atoms, linear or branched perfluoroalkyl with 1 to 21 carbon atoms, or cyano; Y is oxygen atom, sulfur atom, or secondary amine; Z is straight chain alkane, divalent organic group, aromatics or Cycloaliphatic of which carbon-number is 6 to 18, or aliphatic groups of which carbon-number is 1 to 10; Rf is linear or branched perfluoroalkyl of which carbon-number is 1 to 21.
In an embodiment, the acrylic ester monomer is presented by the general expression CH2═CA1COOA2, where A1 is hydrogen atom, methyl, or halogen atoms other than fluorine atom; A2 is CnH2n+1 alkyl, wherein n is between 1 and 30.
In an embodiment, the acrylic ester monomer is selected from the group consisting of
In an embodiment, the molding releasing agent further includes silicon oil.
In an embodiment, the silicon oil is selected from the group consisting of dimethyl silicone oil, methyl chloride silicon oil, methylphenyl silicone oil, and organic denatured silicone oil.
In an embodiment, the silicon oil is selected from the group consisting of
where R is alkylidene radical which has one or more carbon atoms; PA is Polyoxyalkylene; x and y are integers, which are one or more.
In an embodiment, the acid monomer is selected from at least one member of the group consisting of carboxylic acid, phosphate group, phosphonic acid group, phosphinic acid group, sulfate, sulfo group, and sulfino.
In an embodiment, further includes Azobisisobutyronitrile or azobisisobutyronitrile HEPTANITRILE.
In an embodiment, the mold releasing agent is solvent-copolymer.
In an embodiment, a solid content of the mold releasing agent is 1% by weight.
None.
A preferred embodiment of the present invention is applied to synthesize a mold releasing agent of fluorine-containing copolymer, wherein the mold releasing agent is copolymerized with the following components: (A) fluorine-containing monomer, (B) acrylic ester monomer, and (C) acid monomer. The fluorine-containing copolymer can be classified as water based copolymer or solvent-copolymer according to its reaction results.
In more details, (A) fluorine-containing monomer is represented by the general expression CH2═C(—X)C(═O)—Y—Z—Rf, where
X is hydrogen atom, monovalent organic group, halogen atoms, linear or branched perfluoroalkyl with 1 to 21 carbon atoms, or cyano; Y is oxygen atom, sulfur atom, or secondary amine; Z is straight chain alkane, divalent organic group, aromatics or Cycloaliphatic of which carbon-number is 6 to 18, or aliphatic groups of which carbon-number is 1 to 10; Rf is linear or branched perfluoroalkyl of which carbon-number is 1 to 21. Here are some examples of Rf listed below, but please be noted that they are not limitations of the present invention:
H2C═CH—C(═O)—O(CH2)2—(CF2)5CF3
H2C═CH—C(═O)—O(CH2)2—(CF2)7CF3
H2C═CH—C(═O)—O(CH2)2—(CF2)9CF3
H2C═CH—C(═O)—O(CH2)2—(CF2)2—CF—(CF3)2
H2C═CH—C(═O)—O(CH2)2—(CF2)4—CF—(CF3)2
H2C═C(CH3)—C(═O)—O(CH2)2—(CF2)5CF3
H2C═C(CH3)—C(═O)—O(CH2)2—(CF2)7CF3
H2C═C(CH3)—C(═O)—O(CH2)2—(CF2)9CF3
H2C═C(CH3)—C(═O)—O(CH2)2—(CF2)2—CF—(CF3)2
H2C═C(CH3)—C(═O)—O(CH2)2—(CF2)4—CF—(CF3)2
H2C═CH—C(═O)—S(CH2)2—(CF2)5CF3
H2C═CH—C(═O)—S(CH2)2—(CF2)7CF3
H2C═CH—C(═O)—S(CH2)2—(CF2)2—CF—(CF3)2
H2C═CH—C(═O)—S(CH2)2—(CF2)4—CF—(CF3)2
H2C═C(CH3)—C(═O)—S(CH2)2—(CF2)5CF3
H2C═C(CH3)—C(═O)—S(CH2)2—(CF2)7CF3
H2C═C(CH3)—C(═O)—S(CH2)2—CF2)2—CF—(CF3)2
H2C═C(CH3)—C(═O)—S(CH2)2—CF2)4—CF—(CF3)2
H2C═CH—C(═O)—NH(CH2)2—(CF2)5CF3
H2C═CH—C(═O)—NH(CH2)2—(CF2)7CF3
H2C═CH—C(═O)—NH(CH2)2—(CF2)2—CF—(CF3)2
H2C═CH—C(═O)—NH(CH2)2—(CF2)4—CF—(CF3)2
H2C═C(CH3)—C(═O)—NH(CH2)2—(CF2)5CF3
H2C═C(CH3)—C(═O)—NH(CH2)2—(CF2)7CF3
H2C═C(CH3)—C(═O)—NH(CH2)2—(CF2)2—CF—(CF3)2
H2C═C(CH3)—C(═O)—NH(CH2)2—(CF2)4—CF—(CF3)2
(B) acrylic ester monomer is represented by the general expression CH2═CA1COOA2, where
A1 hydrogen atom, methyl, or halogen atoms other than fluorine atom; A2 is CnH2n+1 alkyl, wherein n is between 1 and 30. Here are some examples of A2 listed below, but please be noted that they are not limitations of the present invention:
As to (C) acid monomer, it is selected from at least one member of the group of carboxylic acid, phosphate group, phosphonic acid group, phosphinic acid group, sulfate, sulfo group, and sulfino. Here are some examples listed below, but please be noted that they are not limitations of the present invention:
After the solvent-copolymer being diluted, silicon oil is optionally added thereinto to improve its lubricating effect, which enhances the releasing performance. The viscosity of said silicon oil at 25° C. is not specifically limited, and the silicon oil can be, more specifically, dimethyl silicone oil, methyl chloride silicon oil, methylphenyl silicone oil, organic denatured silicone oil, etc., but not limited as what we mentioned here. Below are more examples:
where
R is alkylidene radical which has one or more carbon atoms; PA is Polyoxyalkylene; x and y are integers, which are one or more.
Add 13.0 g of CF3CF2(CF2CF2)2CH2CH2OCOCH═CH2, 2.0 g of stearyl acrylate, 5 g of acrylic acid, and 30.0 g of isopropanol into a 250 ml glass reaction flask, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile HEPTANITRILE therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of a gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the following test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
<Test Method>
<Judging Standard of Releasing Performance>
Every time a molding is produced, we define the procedure as a molding operation. Longevity of a mold releasing agent is defined as the number of times that a molding can be pulled out of the mold with 3 or higher scores since the tested mold releasing agent is coated on the mold. The releasing performance drops sharply as the count of molding operation performed gets closer to the number of times presented by the longevity. For every mold releasing agent, before its count of molding operation performed actually reaches the number of times presented by the longevity, the releasing performance of each mold releasing agent is roughly the same. Therefore, the releasing performance of each mold releasing agents obtained in the preferred embodiments and the comparative examples listed in Table 1 and Table 2 is the highest score judged by the aforementioned standard in the test method, which is the score judged at the first time of performing a molding operation.
Add 16.0 g of CF3CF2(CF2CF2)2CH2CH2OCOCH═CH2, 3.0 g of lauryl acrylate, 7.0 g of acrylic acid, and 30.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile HEPTANITRILE therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 13.0 g of CF3CF2(CF2CF2)3CH2CH2OCOCH═CH2, 2.5 g of stearyl acrylate, 5.0 g of acrylic acid, and 30.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile HEPTANITRILE therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 12.0 g of CF3CF2(CF2CF2)nCH2CH2OCOCH═CH2 (1.5% n=2, 65% n=3, 18% n=4, 3.5% n=5, 1.4% n=6), 1.0 g of lauryl acrylate, 5.0 g of acrylic acid, and 6.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 6.0 g of CF3CF2(CF2CF2)2CH2CH2OCOCH═CH2, 7.0 g of CF3CF2(CF2CF2)3CH2CH2OCOCH═CH2, 1.0 g of lauryl acrylate, 5.0 g of stearyl acrylate, 5.0 g of acrylic acid, and 60.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 11.0 g of CF3CF2(CF2CF2)2CH2CH2OCOCH═CH2, 1.0 g of lauryl acrylate, 2.0 g of acrylic acid, and 60.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 9.0 g of CF3CF2(CF2CF2)nCH2CH2OCOCH═CH2(1.5% n=2, 65% n=3), 3.0 g of stearyl acrylate, 6.0 g of acrylic acid, and 60.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 12.0 g of CF3CF2(CF2CF2)2CH2CH2OCOCH═CH2, 5.0 g of acrylic acid, and 30.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 11.0 g of CF3CF2(CF2CF2)2CH2CH2OCOCH═CH2, 2.0 g of lauryl acrylate, 4.0 g of phosphoric acid Bis(2-methacryloyloxyethyl) hydrogen phosphate, and 30.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile HEPTANITRILE therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 14.0 g of CF3CF2(CF2CF3CF2(CF2CF2)nCH2CH2OCOCH═CH2 (1.5% n=2, 65% n=3, 18% n=4, 3.5% n=5, 1.4% n=6), 1.5 g of stearyl acrylate, 5.0 g of phosphoric acid Bis(2-methacryloyloxyethyl) hydrogen phosphate, and 6.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Add 10.0 g of CF3CF2(CF2CF2)3CH2CH2OCOCH═CH2, 2.0 g of CF3CF2(CF2CF2)4CH2CH2OCOCH═CH, 1.0 g of stearyl acrylate, 3.5 g of acrylic acid, and 60.0 g of isopropanol into the same kind of flask used in the first preferred embodiment, and heat the flask to 60° C. After that, add 0.2 g of azobisisobutyronitrile therein to perform polymerization reaction at 60° C. for 8 hours. According to analysis results of the gas chromatography, the conversion rate of the produced polymer is higher than 95%. The obtained fluorine-containing copolymer (20 g) is blended with silicon oil (20 g) and acetone (60 g), and then being tested with the aforementioned test method to evaluate releasing performance and longevity thereof. The test result is listed in Table 1.
Respectively add 2.0 g of ammonia into the polymer solutions obtained in the first to the seventh preferred embodiments, remove contained isopropanol by reduced pressure distillation, and then dilute the solution with water until the solid contents therein becomes 3% by weight. The releasing performance and the longevity of each mold releasing agent of these embodiments are tested with the aforementioned test method, and are listed in Table 2.
Respectively add 2.0 g of ammonia into the polymer solutions obtained in the comparative examples 1-4, remove contained isopropanol by reduced pressure distillation, and then dilute the solution with water until the solid contents therein becomes 3% by weight. The releasing performance and the longevity of each mold releasing agent of these embodiments are tested with the aforementioned test method, and are listed in Table 2.
According to the aforementioned preferred embodiments and comparative examples, the mold releasing agent provided in the present invention, which is copolymerized with fluorine-containing monomer, acrylic ester monomer, and acid monomer, is able to replace the conventional compounds of long-chain perfluoroalkyl group to avoid the problem that the conventional compounds of long-chain perfluoroalkyl group would be degraded to PFOA in certain conditions, and the releasing performance and longevity is still comparable.
It must be pointed out that the embodiments described above are only some preferred embodiments of the present invention. All equivalent formulas which employ the concepts disclosed in this specification and the appended claims should fall within the scope of the present invention.
