JPH0377207B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL FIELD OF APPLICATION The present invention relates to an anti-adhesive agent, and more particularly to an anti-adhesive agent for resins, especially epoxy resins. In addition, the anti-adhesion agent of the present invention not only prevents the adhesion of resins such as epoxy resins, but also has functions such as preventing leakage and adhesion of other highly adhesive resins, lubricating oil, water, etc. It is useful for various uses such as adhesion prevention agent for printing ink, anticorrosion and rust prevention for precision machinery, and water and oil repellent. BACKGROUND ART The surfaces of ceramic capacitors, chemical capacitors, film capacitors, etc. are mainly coated with resin such as epoxy resin from the viewpoints of moisture resistance, aesthetics, and protection. Generally, resin such as epoxy resin adheres to the capacitor lead wire due to coating with resin such as epoxy resin, but due to the miniaturization and weight reduction of electronic devices due to advances in integrated circuit technology, accurate dimensional accuracy is required for the capacitor itself. It is also required that resin such as epoxy resin not adhere to the lead portion at all. Conventionally, various anti-adhesion agents have been used to prevent adhesion to the lead wires. For example, silicone-based materials or fluorine-based materials (JP-A-56-53116 and JP-A-55-116782) are exemplified. Problems to be solved by the invention However, silicone-based anti-adhesion agents
Not only does it have poor adhesion prevention properties for resins such as epoxy resins, but it also has poor solder properties and has the drawback of poor conductivity due to the silicone adhesion preventive agent remaining on the lead wires. Fluorine-based anti-adhesion agents have low critical surface tension, so they have excellent anti-adhesion properties and also have excellent solder properties. However, many of these anti-adhesion agents are soluble in organic solvents other than fluorocarbons, such as toluene and xylene, and since resins such as epoxy resins are dissolved in these organic solvents and applied, it is difficult to prevent adhesion. This has the disadvantage that the agent dissolves in the epoxy resin coating, hindering the formation of a uniform coating film on the surface of the capacitor during bulk work on the line, and causing uneven coating or coating defects. The present invention improves the above-mentioned drawbacks by producing a fluorine-based resin that has excellent adhesion prevention properties for resins such as epoxy resins, excellent solder properties, and is insoluble in solvents for resins such as xylene and benzene. Provided is an anti-adhesive agent containing. Means for Solving the Problems That is, the present invention solves the problem using the general formula (): (In the formula, X represents a halogen atom, and a is 0 to 4
perfluoroalkenyl polyvinyl phenyl ether in which at least a _part of the hydroxyl groups of _{polyvinylphenol} represented by Formula (2): CH ₂ = CRCOOC ₂ H ₄ Rf ...(2) (In the formula, R is H or CH ₃ and Rf is
About _{10 %} of the fluorine-containing acrylic monomer represented by:
The present invention relates to an anti-adhesive agent prepared by dissolving a reaction product obtained by reacting at a weight ratio of 1 to about 1:10 in a diluent solvent. The perfluoroalkenyl polyvinyl phenyl ether used in the present invention is obtained by reacting polyvinylphenol (hereinafter collectively referred to as polyvinylphenols), which may have a halogen atom bonded to the phenyl group, with perfluoroolefin. The raw material polyvinylphenols can be obtained by thermally polymerizing p-ethylphenol simultaneously with dehydrogenation, or by substituting the phenyl group of the polymer with halogen by a conventional method. Preferred halogens are chlorine, bromine, and iodine, and the number of substituents is 1 to 4, preferably 1 or 2. Perfluoroolefins are tetrafluoroethylene oligomers, hexafluoropropenes and/or oligomers thereof. In particular, tetrafluoroethylene oligomer has a polymerization degree of 2 to 7, and hexafluoropropene oligomer has a polymerization degree of 2 to 4.
These are preferred for application to various processing agents. Tetrafluoroethylene oligomers or hexafluoropropene oligomers can be obtained by oligomerizing tetrafluoroethylene or hexafluoropropene by the methods described in, for example, US Pat. No. 3,403,191 and US Pat. No. 2,918,501. The oligomers are highly branched compounds consisting of many isomers. The reaction between polyvinylphenols and perfluoroolefin may be carried out in accordance with the reaction method for phenols and perfluoroolefin described in, for example, British Patent No. 1143927 and British Patent No. 1130822. The reaction between polyvinylphenols and perfluoroolefin can be carried out arbitrarily in a ratio of perfluoroolefin to phenolic hydroxyl group that is less than the stoichiometric amount. The perfluoroalkenyl group of the perfluoroalkenyl polyvinyl phenyl ether used in the present invention preferably contains 20% or more of the phenolic hydroxyl group. Average molecular weight of perfluoroalkenyl polyvinyl phenyl ether (based on weight, same below)
is preferably within the range of 1500 to 10000. Preferred perfluoroalkenyl polyvinylphenyl ethers used in the present invention have the following formula: (In the formula, R _f ' is a C _6-9 F _11-17 perfluoroalkenyl group, and n is a number from 10 to 85.) Particularly suitable fluorine-containing acrylic monomers CH ₂ =CRCOOC ₂ H ₄ Rf used in the present invention are CH ₂ =CHCOOC ₂ H ₄ C ₈ F ₁₇ and CH ₂ =C(CH ₃ ).
COOC ₂ H ₄ C ₈ F ₁₇ , CH ₂ =CHCOOC ₂ H ₄ C ₇ F ₁₅ and CH ₂ =C(CH ₃ )COOC ₂ H ₄ C ₇ F ₁₅ . The perfluoroalkenyl polyvinyl phenyl ether and the fluorine-containing acrylic monomer are usually reacted in a weight ratio of about 10:1 to about 1:10, particularly preferably 5:1 to 1:5. This reaction is usually carried out under an inert gas atmosphere such as nitrogen gas, depending on the reactivity of the reaction components and the reaction method.
This is done at 70-100℃ for about 4-24 hours. The reaction method is not particularly limited and may be any of solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, etc., but a particularly preferred method is solution polymerization. Solution polymerization involves dissolving the above reaction components in a suitable organic solvent and adding an organic peroxide (e.g. benzoyl peroxide, di-t-butyl peroxide, t-
Butyl perisobutyrate, azo compounds such as 2,2'-azobisisobutyronitrile, methyl-
2,2'-azobisisobutyrate, etc.) or irradiation with ionizing radiation. Suitable organic solvents are fluorine-based organic solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane, metaxylene hexafluoride, paraxylene hexafluoride, and the like. The copolymers thus obtained are typically about
It is used as an anti-adhesive agent when diluted to 0.5% by weight or more, particularly about 1.0 to 2.0% by weight. Preferred diluent solvents are the above-mentioned fluorine-based organic solvents. Hereinafter, the present invention will be explained with reference to Examples. Examples Example 1 A solution of 30 g of CH ₂ = CHCOOC ₂ H ₄ C ₈ F ₁₇ and 3.0 g of 4-(perfluorohexenyloxy) styrene polymer (average molecular weight approximately 5000) dissolved in 33 g of meta-xylene hexafluoride is sealed. After replacing the air in the container with nitrogen gas, 1.4 g of benzoyl peroxide was added, and the mixture was left sealed at 70°C for 24 hours.
66 g of meta-xylene hexafluoride solution containing 50% copolymerization product was obtained. Example 2 A solution prepared by dissolving 16 g of CH ₂ =CHCOOC ₂ H ₄ C ₈ F ₁₇ and 48 g of 4-(perfluorohexenyloxy)styrene polymer (average molecular weight approximately 5000) in 64 g of meta-xylene hexafluoride was prepared using a stainless steel machine equipped with a stirrer. After replacing the air in the container with nitrogen gas, 0.6 g of benzoyl peroxide was added and the mixture was stirred in a sealed container for 24 hours at 100°C. 128 g of ride solution was obtained. Examples 3 to 20 According to the procedure of Example 1, various copolymers of fluorine-containing acrylic monomer and 4-(perfluoroalkenyloxy)styrene polymer were obtained according to the reaction weight ratios shown in Table-1. Ta. Anti-adhesion test The samples obtained in Examples 1 to 20 above were tested in 1, 1, 2
- Trichloro-1,2,2-trifluoroethane dissolved to prepare 0.5% by weight anti-stick agent, epoxy resin or acrylic/epoxy (1:1)
The adhesion prevention property to resin was investigated. Table 2 of the results
Shown below. Comparative Examples 1 and 2 For comparison, a polymer having the following formula (10% by weight)
The adhesion prevention properties were investigated using CCl ₂ FCClF ₂ solution).
The results are shown in Table-2. Comparative Examples 3 and 4 Two homopolymers were prepared according to the procedure of Example 1, except that CH ₂ =CHCOOC ₂ H ₄ C ₈ F ₁₇ or 4-(perfluorohexenyloxy)styrene polymer was used as the reaction component. A meta-xylene hexafluoride solution was prepared. These samples were subjected to the anti-adhesion test described above, and the results are shown in Table 2. Comparative Example 5 Meta-xylene hexafluoride solutions containing equal weight mixtures of the two homopolymers prepared in Comparative Examples 3 and 4 were subjected to the anti-adhesion test described above, and the results are shown in Table 2.

【table】

【table】

[Table] Effects of the Invention The anti-adhesion agent of the present invention effectively prevents the adhesion of resins such as epoxy resins. Also, the solder properties are extremely good. Furthermore, it does not dissolve in ordinary organic solvents and has almost no adverse effect on resin coatings such as epoxy resins.

Claims (1)

[Claims] 1 General formula (1): (In the formula, X represents a halogen atom, a represents a number from 0 to 4, and n represents a number from 10 to 85) At least a part of the hydroxyl groups of polyvinylphenol are perfluoroolefin C _{6 to 9} F Perfluoroalkenyl polyvinyl phenyl ether etherified by _{12 to 18} and general formula (2): CH ₂ = CRCOOC ₂ H ₄ Rf ... (2) (wherein, R is H or CH ₃ , Rf is
About _{10 %} of the fluorine-containing acrylic monomer represented by:
An anti-adhesive agent prepared by dissolving a reaction product obtained by reacting at a weight ratio of 1 to about 1:10 in a diluent solvent. 2. The anti-adhesion agent according to item 1, wherein the concentration of the reaction product is 0.5 to 10% by weight.