JPH06136230A - Fluororesin composition - Google Patents

Abstract

PURPOSE:To improve adhesion of a fluororesin, especially perfluoro2,2- dimethyl-1,3-dioxol polymer to a substrate. CONSTITUTION:This fluororesin composition is obtained by adding 0.005-10 pts.wt. aminosilane to 100 pts.wt. fluororesin. Perfluoro-2,2-dimethyl-1,3-dioxol- based polymer can be applied to a substrate, but its adhesion is poor. The adhesion to the substrate can remarkably be improved by adding the aminosilane which is not fluorinated to the perfluoro-2,2-dimethyl-1,3-dioxol-based polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoropolymer composition, and particularly to other substrates such as woven glass cloth, aluminum plate, iron plate, plastic molded product, organic or inorganic optical fiber and the like. The present invention relates to a fluororesin composition having excellent adhesion.

[0002]

2. Description of the Related Art Fluoropolymers containing perfluoro-2,2-dialkyl-1,3-dioxole as a main constituent are WO
89/12240 gazette and WO89 / 11495 gazette, it has extremely good heat resistance,
It is characterized by being a low-refractive-index polymer, and its applications are being developed as electronic materials, optical materials, and the like. This polymer has a major feature that it has a high fluorine content, but on the other hand, it has a difficulty in adhesion to other substrates.

A method for improving the adhesion of a perfluoropolymer to another substrate is disclosed in Japanese Patent Application Laid-Open No. 2-153964.
A composition containing a compound having a functional group such as -OR, -COOH, -SO3H and a fluorinated hydrocarbon group as a coupling agent, and according to the present invention, the adhesion to other base materials of perfluoropolymer is improved. Significantly improved.

[0004]

[Problems to be Solved by the Invention] WO89 / 12240
A solution prepared by dissolving the perfluoropolymer shown in the publication in perfluoro (2-butyltetrahydrofuran) which is a solvent [Fluorinate FC-75 manufactured by 3M Co., Ltd.] is applied on a glass plate, and the dried coating film is on the glass plate Although it is apparently in close contact with it, it has the drawback of peeling off when scratched with a nail. The invention disclosed in Japanese Unexamined Patent Publication No. 153964/1990 is based on a perfluoropolymer and has a functional group such as -OH, -OR, -COOH and a fluorinated hydrocarbon group such as 3,3,3-trifluoropropyltrimethoxy. The coating film formed on the glass plate using the composition containing silane has much improved adhesion to the glass substrate as compared with the coating film formed on perfluoropolymer without the addition of a coupling agent. When the eye peeling test is performed, there is a problem that 50% or more of the corrugated coating is peeled off.

[0005]

The inventors of the present invention, while studying to obtain a fluororesin composition free from the above-mentioned difficulties, unexpectedly found that a non-fluorine-containing silane coupling agent containing an amino group was used as a binder. The present invention has been completed by finding that the compatibility with a fluoropolymer is excellent, and that the adhesion of the perfluoropolymer to other substrates can be improved, and the gist of the invention is perfluoro-2, 2-
Aminosilane is added in an amount of 0.005 to 100 parts by weight of a fluoropolymer mainly composed of dialkyl-1,3-dioxole.
A fluoropolymer composition is characterized by being added in a ratio of 10 parts by weight.

The perfluoro-2,2-dialkyl-1,3-dioxole-based fluoropolymer used in the practice of the present invention is perfluoro-2,2-dimethyl-1,3-
It is a polymer containing 20 to 100% by weight of dioxole and 80% by weight or less of other copolymerizable unsaturated compound, and has a glass transition temperature of 80 ° C or higher, preferably up to about 300 ° C. , Especially perfluoro-2,2-dimethyl-
The copolymerization amount of 1,3-dioxole is 40% by weight or more,
Amorphous polymers having a single glass transition temperature are preferred. As the copolymerizable compound, tetrafluoroethylene, chlorotrifluoroethylene, ethylene, CF ₂ =
CFOCF ₃ , CH ₂ = CF ₂ , CF ₂ = CFCF ₃ , CH ₂ = CHF, CH ₂ = CHR
_{and f 2} (R _f : perfluoroalkyl group), CF ₂ ═CFOQA (Q is perfluoroalkyl ether, A is —COOC _n F _{2n + 1} , and n is an integer of 1 to 4) and the like.

The aminosilane used in carrying out the present invention is represented by the chemical formula [1], the chemical formula [2] or the chemical formula [3].
Can be used, and aminosilanes containing two or more amino groups can also be used.

[Chemical 1]

[Chemical 2]

[Chemical 3]

It is an important requirement that the aminosilane molecule represented by [Chemical Formula 1], [Chemical Formula 2] or [Chemical Formula 3] does not contain a fluorine atom, and these non-fluorinated aminosilanes have a reason. Although it is unknown, the compatibility with the fluoropolymer is good, the film formed from the fluororesin composition of the present invention, aminosilane does not bleed out from the coating material, relative to the substrate The adhesiveness of the fluororesin composition molded product is also very good.

The addition ratio of aminosilane to the fluororesin is in the range of 0.005 to 10 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the fluororesin. A fluororesin composition in which the amount of aminosilane added to 100 parts by weight of the fluororesin is less than 0.005 is not preferable because the adhesion to the base material is not significantly improved when applied to the base material.
On the other hand, a fluororesin composition obtained by adding 10 parts by weight or more of aminosilane to 100 parts by weight of the fluororesin has good adhesion to the substrate, but the characteristics of the fluororesin itself are impaired, which is not preferable.

The fluororesin composition of the present invention comprises another substrate,
For example, it has excellent adhesion to synthetic fibers, glass fibers, optical fibers, plastic plates, metal plates, etc., and utilizes the properties of fluororesins such as low dielectric properties, low refractive index, water repellency, and oil repellency. Thus, it can be used in a wide variety of fields as a printed circuit board material, an optical fiber sheath material, a water-generating agent, an oil-generating agent and the like.

[0011]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The method of evaluating the adhesion of the coating film used in these examples to the substrate was according to the following method.

[Method for evaluating adhesion of coating film] According to JIS-K-5400, a solution prepared by dissolving a fluororesin in perfluoro (2-butyltetrahydrofuran) was coated on a glass substrate to give a film thickness of 50 μm.
1 mm with a cutter knife on the coated surface so that it becomes m.
^After making 100 ^second cells and adhering the adhesive tape on these cells, the adhesive tape was peeled off, and the adhesiveness was judged according to the number of cells remaining on the substrate.

[0013]

Example 1 10 parts by weight of a fluorocopolymer [I] consisting of 68 mol% of perfluoro-2,2-dimethyl-1,3-dioxole and 32 mol% of tetrafluoroethylene was added to perfluoro (2-
(Butyltetrahydrofuran) 40 parts, and a solution containing aminosilane shown in [Table 1] was applied onto a glass plate by a roll coating method so that the film thickness was 50 μm, and dried. The results of evaluating the adhesion of these coating films are shown in [Table 1].

[Table 1]

[0014]

Example 2 In No. 5 of [Table 1] in Example 1, except that H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ was used as the aminosilane.
When a coating film was formed on a glass plate in exactly the same way and a peeling test of the coating film was performed, no further peeling of the coating film occurred,
The residual rate of the coating film on the glass plate was 100/100.

[0015]

Example 3 A coating film was formed by using the fluororesin composition shown in No. 4 in Example 1 [Table 1] as a substrate and shown in [Table 2], and its adhesion was measured. The results obtained are shown in [Table 2].

[Table 2]

Claims (2)

[Claims] 1. Aminosilane or a condensate thereof is added in an amount of 0.005 to 10 to 100 parts by weight of a fluoropolymer containing perfluoro-2,2-dialkyl-1,3-dioxole as a main constituent unit.
A fluororesin composition characterized by adding parts by weight. 2. A fluororesin composition which is a non-fluorine-containing aminosilane having a primary amino group or a condensate thereof as the aminosilane compound.