JPH0364555B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to prevention of adhesion of epoxy resin, and more particularly, the present invention relates to a method for preventing excess epoxy resin from adhering to lead wires when coating the surface of a capacitor with epoxy resin, an anti-adhesion agent, and an anti-adhesion agent. Regarding the composition. Epoxy resin is often used as a moisture-proof protective material for ceramic capacitors, chemical capacitors, etc., but the surface of the capacitor is coated with such a moisture-proof protective material by dipping the capacitor in the moisture-proofing agent, pulling it out, and curing it. . However, during coating, epoxy resin may adhere to the lead wires attached to the capacitor body, but if you try to mount such a capacitor on a printed circuit board, for example, the epoxy resin adhering to the lead wires may become an obstacle. This may cause problems such as not being able to wire properly. As shown by the fact that epoxy resin is frequently used as an adhesive, it has a strong adhesive force to lead wires, and once attached, cannot be easily removed. Conventionally, silicone oil emulsions have been used to prevent epoxy resin from adhering to lead wires.
The so-called liquid drainability was insufficient, and a satisfactory effect could not be obtained. In addition, in order to increase the effectiveness, if the concentration of silicone oil is increased and it is applied to the lead wires, a thin film is formed on the lead wires due to the creeping property of the silicone oil. The disadvantage was that electrical conduction failure occurred at the connecting parts of the conductor wires, causing malfunction of the assembled device. The present inventors focused on these problems associated with capacitor manufacturing, and developed a method and anti-adhesive agent to prevent epoxy resin from adhering to lead wires during capacitor manufacturing, and even if it does adhere, it can be easily removed with a fingertip etc. As a result of repeated research into an anti-adhesive agent that doubles as a mold release agent to allow the epoxy resin to separate,
A copolymer consisting of less than 90% to 80% by weight of a polymerizable compound containing a perfluoroalkyl group having 4 to 21 carbon atoms and more than 10% by weight of a compound copolymerizable therewith has been conventionally used as an anti-adhesion agent. The present invention was completed based on the discovery that it is much more effective than the silicone oil emulsions that have been used in the past. That is, the gist of the present invention consists of a polymerizable compound containing a perfluoroalkyl group having 4 to 21 carbon atoms and a compound copolymerizable therewith;
An anti-adhesion agent for epoxy resins consisting of a copolymer in which the proportion of the latter is less than 90 to 80% by weight and the latter is more than 10 to 20% by weight, an anti-adhesion agent prepared by dispersing the copolymer in water or dissolving it in an organic solvent. The present invention relates to a composition and a method of applying the composition to a substrate and then drying off the water or solvent to impart epoxy resin adhesion prevention properties to the substrate. When applying the anti-adhesion agent of the present invention to a substrate, such as a metal wire, even if epoxy resin adheres to the substrate, it can be removed at least with the fingertips. Furthermore, even when the base body, for example, the metal wire, is connected to another metal by soldering, it does not have any adverse effect on the soldering characteristics, and does not cause poor electrical conductivity. The polymerizable compound containing a perfluoroalkyl group having 4 to 21 carbon atoms used in the present invention includes various compounds having a perfluoroalkyl group having 4 to 21 carbon atoms. Specifically, for example, the formula: (2) Rf(CH ₂ )nOCOCR″=CH ₂ (6) RfCH=CH( _CH2 )nOCOCR''= _CH2 [wherein, Rf is a perfluoroalkyl group having 4 to 21 carbon atoms; R is hydrogen or an alkyl group having 1 to 10 carbon atoms; R' is the number of carbon atoms 1-10 alkylene group; R'' is hydrogen or a methyl group; R is an alkyl group having 1-17 carbon atoms; n represents an integer of 1-10. ] Examples include compounds having a perfluoroalkyl group having 4 to 21 carbon atoms at one end and a carbon-carbon double bond at the other end. There are various compounds that can be copolymerized with the above compounds, but the main ones are (1) acrylic acid, methacrylic acid, and their methyl, ethyl, butyl, isobutyl, propyl, 2-ethylhexyl, hexyl, and decyl , lauryl, stearyl, β-hydroxyethyl, glycidyl esters, (2) vinyl esters of fatty acids such as acetic acid, propionic acid, caprylic acid, lauric acid, and stearic acid, (3) styrene, α-methylstyrene, p-
Styrenic compounds such as methylstyrene, (4) vinyl halides or vinylidene compounds such as vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, (5) allyl heptanoate, allyl caprylate, capron Allyl esters of fatty acids such as allyl acids, (6) vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone, (7) N-methylacrylamide, N-methylolmethacrylamide, glycidyl acrylate,
Examples include acrylamides such as glycidyl methacrylate and dienes such as (8)2,3-dichloro-1,3-butadiene and isoprene. Among these, acrylic esters, methacrylic esters and styrene compounds are particularly preferred from the viewpoint of ease of copolymerization. The proportion of the polymerizable compound containing a perfluoroalkyl group and the compound copolymerizable therewith in the copolymer is less than 90 to 80% by weight of the former and more than 10 to 20% by weight of the latter, and the amount of the latter The performance decreases as the value increases, but in this range,
Much better epoxy resin adhesion prevention properties can be obtained than conventionally used silicone oil emulsions. The polymerization reaction method for producing the polymer used in the present invention can be arbitrarily selected, and any of various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and radiation polymerization can be adopted. For example, a mixture of compounds to be copolymerized is dissolved in a suitable organic solvent and subjected to solution polymerization under the action of a polymerization initiation source (such as a peroxide, an azo compound, or ionizing radiation that is soluble in the organic solvent used). Alternatively, a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant and emulsion polymerized by the action of a polymerization initiator such as a peroxide, an azo compound, or ionizing radiation. The surfactant used may be anionic, cationic or nonionic. The anti-adhesion agent of the present invention is a polymer used in the present invention.
It is used by dissolving 0.2 to 3% by weight, preferably 0.5 to 1.5% by weight in an organic solvent or dispersing it in water with a suitable emulsifier. Suitable solvents include fluorine-based solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane, and metaxylene hexafluoride. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, with cationic and nonionic emulsifiers being particularly preferred. Desirable anionic emulsifiers have 16 to 18 carbon atoms.
Sodium salt of sulfated alkenyl acetate,
Sodium oleate, sodium salt of sulfated methyl oleate, ammonium ω-H-polyfluoroalkanoate having 8 to 10 carbon atoms, ammonium perfluoroalkanoate, carbon number 10 to 18
Alkyl sodium sulfate, carbon number 12 ~
18 sodium alkylbenzene sulfonate,
and sodium alkylnaphthalene sulfonate. Desirable cationic ones are
(dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, N-[2-(diethylamino)ethyl]-oleamide hydrochloride, dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium chloride, and trimethyloctadecyl Includes ammonium chloride and the like. Desirable nonionic emulsifiers include ethylene oxide, hexylphenol, isooctylphenol, hexadecanol, oleic acid, and
It includes condensation products with 16 alkanethiols, alkylamines having 12 to 18 carbon atoms, and the like. To impart anti-stick properties to a substrate, it is sufficient to immerse the substrate, for example the leads of a capacitor, in the inhibitor composition and allow it to air dry. It is preferable to use a solution type composition because of the ease of air drying and the ease with which the liquid is compatible. Next, the present invention will be explained in more detail by showing Examples and Comparative Examples. In each example, parts or %
Unless otherwise specified, parts or percentages are by weight.
represents. Example 1 16 g of CF ₃ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH=CH ₂ and 4 g of styrene were dissolved in a mixed solution of 20 g of acetone and 60 g of meta-xylene hexafluoride,
The mixture was placed in a 200 ml four-necked flask, and after replacing the air inside with nitrogen gas, 0.3 g of a 70% t-butyl peroxyvivalate solution in paraffin was added dropwise, and a polymerization reaction was carried out at 55°C for 8 hours. This polymerization reaction yielded 98 g of a solution containing 196% of a copolymer containing 20% by weight of styrene. Example 2 25.5g, emulsifier (dimethyloctadecylamine acetate) 1.5g, acetone 15g and water 165g.
Pour into a 300 ml four-necked flask, replace the air inside with nitrogen gas while stirring, and heat on a water bath. When the internal temperature reached 55℃, a solution of 0.2 g of azobisisobutyramidine hydrochloride in 10 g of water was added dropwise.
Keep the internal temperature at 60℃ and continue the polymerization reaction for 2 hours. 207 g of an emulsified dispersion containing 14.2% of a copolymer of 85% by weight and 15% by weight of lauryl methacrylate was obtained. The polymers used in the following Examples 3 to 11 and Comparative Examples 4 to 8 were those obtained in Example 1 or 2, or those produced by the same procedure as Examples 1 and 2. Examples 3 to 11 and Comparative Examples 1 to 8 2 cm from the end of 7 cm of capacitor lead wire
The parts shown in Table 1 are dipped in each of the anti-adhesion compositions shown in Table 1, and dried at room temperature until the solvent or water is removed. After dipping 5 cm from the end of the lead wire coated with the anti-adhesion agent into the epoxy resin composition for capacitors and pulling it up, it was left at room temperature for 10 minutes, and then
Curing is performed in a constant temperature bath at 120°C for 1 hour. The portion of the surface of each lead wire treated with the anti-adhesion agent was observed, and whether or not the epoxy resin was adhered to the surface was visually determined according to the following criteria. The results are shown in Table 1. Judgment Criteria: There is no epoxy resin attached to the area where the anti-adhesion agent has been applied, or the epoxy resin is attached in spots but can be removed with the fingertips. × The effect of the anti-adhesion agent is not strong, and the epoxy resin adheres to the areas where it is not applied.

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Claims (1)

[Scope of Claims] 1 Consists of a polymerizable compound containing a perfluoroalkyl group having 4 to 21 carbon atoms and a compound copolymerizable therewith, in which the former is less than 90 to 80% by weight and the latter is more than 10 to 20% by weight. An anti-adhesive agent for epoxy resins consisting of a copolymer in a proportion of % by weight. 2 The copolymerizable compound is an acrylic ester,
The anti-adhesion agent according to claim 1, which is a methacrylic acid ester or a styrene compound. 3 Consists of a polymerizable compound containing a perfluoroalkyl group having 4 to 21 carbon atoms and a compound copolymerizable therewith, the former being less than 90 to 80% by weight and the latter being more than 10 and 20% by weight An anti-adhesion agent composition for epoxy resin, characterized in that a copolymer is dispersed in water or dissolved in an organic solvent. 4. The composition according to claim 3, wherein the polymer is a polymer using an acrylic ester, a methacrylic ester, or a styrene compound as a copolymerizable compound. 5 Consisting of a polymerizable compound containing a perfluoroalkyl group having 4 to 21 carbon atoms and a compound copolymerizable therewith, the former being less than 90 to 80% by weight and the latter being more than 10 and 20% by weight Adhesion for epoxy resin to a substrate characterized by dispersing the copolymer in water or dissolving it in an organic solvent, applying the resulting dispersion or solution to the substrate, and then drying and removing the water or organic solvent. How to impart preventive properties. 6 The copolymerizable compound is an acrylic ester,
6. The method according to claim 5, which uses a polymer that is a methacrylic acid ester or a styrene compound.