KR850001736B1 - The manufacturing method of adhesive preventing reagent of epoxy resin - Google Patents

Abstract

In the case of coating the condenser surface, the adhesive resistant reagent prevents the excess epoxy resin from adhering to the wire. The adhesive resistant reagent consists of a 100-90 wt.% polymerizable compound and a 0-10 wt.% copolymerizable compound. The polymerizable compound containined the perfluoro alkyl group with a carbon number or 4-21. The copolymerizable compound was acrylic acid, vinyl ester of aliphatic acid, styrene, vinyl alkyl ketone, diene, etc. This reagent improves on adhesive resistivity and ease of removal.

Description

Manufacturing method of epoxy resin adhesion inhibitor

The present invention relates to a method for producing an epoxy resin adhesion inhibitor. In more detail, when the epoxy resin is coated on the surface of the condenser, the present invention relates to a method for preparing an anti-sticking agent that prevents excess epoxy resin from adhering to the conductive wire. Epoxy resins are widely used as moisture-proof protective materials such as ceramic capacitors and chemical capacitors. However, the coating of the surface of the capacitors by moisture-proof protective materials has been carried out by immersing the capacitors in a desiccant, and then curing them.

Epoxy resins may be attached to the conductors connected to the condenser body during such coating operations.However, if such a capacitor is attached to a printed circuit board, for example, the epoxy resin attached to the conductors may be disturbed and wiring cannot be satisfactorily performed. There is a case.

As can be seen from the widely used adhesives, the epoxy resin has a strong adhesive force to the conductor, so once it is attached, it cannot be easily separated.

Conventionally, silicone oil emulsions and the like have been used for the purpose of preventing adhesion of epoxy resins to conductive wires. However, the adhesion resistance of epoxy resins is insufficient, and a satisfactory effect cannot be obtained.

In addition, if the concentration of silicon oil is increased and attached to the conductor to increase the effect, a thin film is formed on the surface of the conductor due to the covering property of the silicone oil. There was a flaw that caused the device to malfunction.

The present inventors have focused on such a problem due to the production of the capacitor, and a method or an anti-sticking agent has been attached even if the epoxy resin is prevented from adhering to the conductor during the production of the capacitor. However, research on the anti-adhesive agent which also releases the epoxy resin to allow the epoxy resin to be easily released by the finger has been conducted. As a result, homopolymers of polymerizable compounds containing 4-21 perfluoroalkyl groups or other polymerizations of up to 10% by weight The present invention has been completed with the discovery that copolymers with possible compounds are extremely effective as anti-sticking agents.

That is, the gist of the present invention is composed of a perfluoroalkyl group-containing polymerizable compound having 4 to 21 carbon atoms and a compound copolymerizable therewith, the anti-sticking agent comprising a polymer having 100-90 wt% of the former and 0-10 wt% of the latter The present invention relates to an anti-adhesive composition in which the polymer is dispersed in water or dissolved in an organic solvent, and the composition is applied to a substrate and then dried by removing water or a solvent to impart anti-adhesion to the substrate.

When the anti-sticking agent of the present invention is applied to a gas, for example, a metal wire, the epoxy resin is not attached to the gas, and even though it is attached, it can be easily separated with a fingertip. For example, the metal wire may be soldered with other metals. In the case of the connection, the soldering characteristics are not adversely affected, and electrical conduction failure is not caused.

As the compound capable of containing a 4-fluoro-carbon perfluoroalkyl group used in the present invention, various compounds having a perfluoroalkyl group of 4-21 carbon atoms are included.

Specifically, for example,

[Wherein Rf is a perfluoroalkyl group having 4-21 carbon atoms: R is hydrogen or an alkyl group having 1-10 carbon atoms: R 'is an alkylene group having 1-10 carbon atoms: R' 'is hydrogen or a methyl group: R "' is 1 carbon Alkyl group of -17, n represents an integer of 1-10], and a compound having a 4-fluoro perfluoroalkyl group on one side and a carbon-carbon double bond on the other side .

There are various kinds of compounds copolymerizable with the above compounds, but as the main compounds,

(1) Acrylic acid, methacrylic acid and their methyl, ethyl, butyl, isobutyl, propyl, 2-ethylhexyl, hexyl, decyl, lauryl, stearyl, β-hydroxyethyl and glycidyl esters.

(2) Vinyl esters of fatty acids, such as vinegar acid, propionic acid, caprylic acid, lauryl acid, and stearic acid.

(3) Styrene compounds, such as styrene, (alpha) -methylstyrene, and P-methylstyrene.

(4) Vinyl halide or vinylidene compounds such as vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride and vinylidene chloride.

(5) Aryl esters of fatty acids, such as aryl heptanolate, aryl caprylate, and aryl capronate.

(6) Vinyl alkyl ketones, such as vinyl methyl ketone and vinyl ethyl ketone.

(7) acrylamides such as N-methylacrylamide, N-methylol methacrylamide, glycidyl acrylate and glycidyl methacrylate, and

(8) dienes such as 2,3, -dichloro-1,3-butadiene and isoprene can be exemplified.

Among these, copolymerization is easy and especially preferable are acrylic acid ester, methacrylic acid ester, and a styrene-type compound.

As for the ratio in the polymer of a perfluoroalkyl-group containing polymerizable compound and the compound copolymerizable with this, the former is 100 to 90 weight%, and the latter is 0 to 10 weight%.

Anti-sticking performance is best in the presence of a small amount of other copolymer compound, and the performance decreases as the amount is increased.

The polymerization method for producing the polymer used in the present invention can be arbitrarily selected, and any one of various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and radiation polymerization can be adopted.

For example, the mixture of compounds to be copolymerized is dissolved in a suitable organic solvent and solution polymerized by the action of a polymerization initiator (peroxide, azo compound or ionizing radiation, etc. soluble in the organic solvent used).

Alternatively, the mixture of the 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 peroxide, azo compound or ionizing radiation.

As surfactant, various things of anionic, cationic, or nonionic are used. The anti-sticking agent of the present invention is used by preparing 0.2-3% by weight of the polymer used in the present invention, preferably 0.5-1.5% by weight, in a composition in which an organic solvent is dissolved or dispersed in water with a suitable emulsifier. Suitable organic solvents include fluorine-based solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane and methaxylene hexafluorolide.

As the emulsifier, various kinds of anionic, cationic or nonionic can be used, and particularly preferred are cationic and nonionic.

-H-폴리플루오로알카노에이트, 암모늄퍼플루오로알카노에이트, 탄소수 10-18의 알킬황산나트륨, 탄소수 12-18의 알킬벤젠술폰산나트륨 및 알킬나프탈렌 술폰산나트륨 등이다.Preferred anionic emulsifiers are sodium salts of alkenyl acetate sulfate of 16-18, sodium oleate, sodium salt of methyl oleate sulfate, ammonium having 8-10 carbon atoms,

-H-polyfluoroalkanoate, ammonium perfluoroalkanoate, sodium alkyl sulfate of 10-18 carbon atoms, sodium alkylbenzenesulfonate of 12-18 carbon atoms and sodium alkylnaphthalene sulfonate.

Further preferred cationic emulsifiers are chloride (dodecylmethylbenzene) trimethylammonium, benzyldodecyldimethylammonium hydrochloride, N- [2- (diethylamino) ethyl] -oreamide, dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride , Hexadecyltrimethylammonium chloride, trimethyloctadecylammonium chloride, and the like.

Further preferred nonionic emulsifiers include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkanediols of 12-16 carbon atoms, alkylamines of 12-18 carbon atoms, and the like.

When imparting anti-adhesion property to a gas, it is sufficient only to immerse the air, for example, the lead of the condenser in the anti-preparation composition, and air-dry it. In view of the ease of air drying and the familiarity of the liquid, a solution type may be used.

Next, an Example and a comparative example are given and this invention is demonstrated further more concretely.

What is indicated by each weight part or% shall express a weight part or weight% unless there is particular notice.

Example 1

32 g of a compound (a mixture of a weight ratio of 4: 2 of a compound having n = 3,4,5), 0.8 g of 2-ethylhexyl methacrylate and 0.8 g of glycidyl methacrylate were added with 23 g of acetone and tetrachlorodifluoro Dissolved in a mixed solvent of 128 g of roethane and 50 g of trichlorotrifluoroethane, the resulting solution was placed in a 300 ml four-necked flask, and the internal air was replaced with nitrogen gas. Then, 3 g of t-butylperoxy pivalate was paraffin 70 % Solution was added dropwise and polymerization was carried out at 55 ° C. for 7 hours.

Next, a solution of 3 g of t-butylperoxy pivalate is added dropwise, and the polymerization is continued at the same temperature for 7 hours.

This polymerization reaction yielded 230 g of a solution containing 14.2% of a polymer.

Example 2

General formula:

30 g of the compound, 1.5 g of an emulsifier (dimethyl octadecylamine acetate), 15 g of acetone, and 165 g of water are placed in a 300 ml four-necked flask, and the inside air is replaced with nitrogen gas and heated in a water. When the internal temperature reached 55 ° C, a 10g solution of 0.2 g of azobisisobutyroamidine hydrochloride was added dropwise, and the polymerization reaction was continued for 2 hours while maintaining the internal temperature at 60 ° C to contain 14% of the homopolymer. 210 g of one emulsion dispersion was obtained.

The polymers used in the following examples are those obtained in Examples 1 or 2 or prepared according to the same procedure as in Examples 1,2.

Example 3-8 and Comparative Example 1-5

A 2 cm portion at the end of 7 cm of the condenser wire is immersed in each of the anti-sticking agent compositions shown in the first table and dried until the solvent or water disappears at room temperature.

5 cm was immersed in the epoxy resin composition for condensers and taken out by the end which apply | coated the anti-sticking agent of this wire, and it is left to stand at room temperature for 10 minutes, and then it hardens for 1 hour in 120 degreeC thermostat.

The application of the anti-sticking agent on the surface of the angle line subjected to the above treatment was observed, and it was visually determined whether the epoxy resin adhered to the surface according to the following criteria, and the results are shown in the first table.

Criteria

◎ Epoxy resin is not attached at all to the coating agent.

○ A small amount of epoxy resin is attached to the application part of the anti-sticking agent, but when the fingertips are touched, it is separated.

△ Epoxy resin is stained and attached to the application part of the anti-sticking agent, but it is easily removed with the tip of a finger.

× The epoxy resin is attached to the same parts that are not applied without any effect of the anti-sticking agent.

[Table 1]

1) Tosirishicon Co., Ltd .: SH-7036

[Examples 9 to 19]

In the same manner as in Examples 3 to 8 and Comparative Examples 1 to 5, a copolymer of CF ₃ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ 95% and the copolymerizable compound 5% shown in Table 2 Epoxy resin adhesion was observed for the CCl ₂ FCClF ₂ solution (concentration 1% by weight).

These results are listed in Table 2.

[Table 2]

Claims (1)

(6) 90% by weight or more of one or more polymerizable compounds (A) selected from compounds represented by RfCH = CH (CH ₂ ) nOCOCR ″ = CH ₂ and acrylic acid, methacrylic acid and their methyl, ethyl and butyl Isobutyl, propyl, 2-ethylhexyl, hexyl, decyl, lauryl, stearyl, β-hydroxyethyl, glycidyl esters; vinegar acid, propionic acid, caprylic acid, lauryl acid, stearyl acid, etc. Vinyl esters of fatty acids, styrene compounds such as styrene, α-methyl styrene, and p-methyl styrene; Fatty acid aryl esters such as aryl heptanolate, aryl caprylate and aryl capronate; vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; acryl such as N-methol methacrylamide and N-methol methacryl amide Amides, and 2,3-dichloro-1,3-butadiene, which Dienes, such as friendly; by polymerizing one or more compounds (B) 10% by weight selected from the reaction process for producing an epoxy resin adhesion preventing agent of the general formula, R _f is a carbon number of 4 to 21 perfluoroalkyl An alkyl group; R is hydrogen or an alkyl group having 1 to 10 carbon atoms; R 'is an alkylene group having 1 to 10 carbon atoms; R''is a hydrogen or methyl group; R "'represents 17 alkyl groups in 1 carbon atom; n represents the integer of 1-10.