JP2007119688A - Fluorine-containing curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing curable composition giving a cured product which exhibits excellent tensile strength and elongation at break. <P>SOLUTION: The curable composition is composed of (A) a fluorine-containing amino compound expressed by formula (3) (in the formula Rf is a divalent perfluoropolyether residue and X is a specific divalent group containing N), and (B) a polyaddition product of a fluorine-containing diol with an epoxy compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fluorine-containing curable composition, and in particular, to a composition containing an epoxy compound having a perfluoroether residue and giving an elastic and soft cured product.

Epoxy resins are widely used for molded products, sealants, adhesives, and the like. However, the cured product is generally hard and tough and lacks flexibility. For example, when used as an adhesive, problems such as warping or cracking or peeling may occur due to a temperature change due to a difference in coefficient of thermal expansion from the substrate to which the adhesive is applied. Moreover, an epoxy resin is inferior in chemical resistance.

アミノシラン化合物とを含み、フッ素ゴムの接着剤として有用な組成物が知られている（特許文献１）。又、末端にビニル基を有するフロロポリエーテルと、エポキシ基を有するシラン化合物を反応させて得られる含フッ素エポキシ化合物が知られている（特許文献２）。 As an improvement of the above epoxy resin problem, the following epoxy compound,

A composition containing an aminosilane compound and useful as an adhesive for fluororubber is known (Patent Document 1). Further, a fluorine-containing epoxy compound obtained by reacting a fluoropolyether having a vinyl group at a terminal with a silane compound having an epoxy group is known (Patent Document 2).

On the other hand, a fluorine-containing amine compound obtained by reacting a diamine with the end of a fluoropolyether is known (Patent Document 3), and a curable composition containing the amine compound and a polyfunctional epoxy compound is disclosed. (Patent Document 4). The composition can be cured relatively easily and is excellent in solvent resistance and chemical resistance.
JP-A-56-79150 JP-A-11-80315 JP 11-92557 A JP 11-92547 A

 However, the curable composition containing the amine compound and the polyfunctional epoxy has room for improvement in terms of tensile strength and elongation at break. In addition, the polyfunctional epoxy compound has a problem that it is difficult to handle because it is not so stable in storage stability. Then, this invention aims at providing the fluorine-containing curable composition improved in these points.

（式中、Ｒｆは２価パーフルオロポリエーテル残基であり、ｍは０〜５の整数であり、Ｘは下記式のいずれかにて示される２価の基である）

（Ｒ²及びＲ³は夫々、互いに独立に、置換されていてよい、炭素数１〜１０の２価炭化水素基であり、Ｒ⁴は互いに独立に、水素原子または炭素数１から６の１価炭化水素基である）
（Ｂ）下記式（１）にて示される含フッ素2価アルコールと下記式（２）にて示されるエポキシ化合物との重付加によって得られ、及び、エポキシ当量が５００〜２５００である含フッ素エポキシ化合物と、

（Ｒｆ”は２価のパーフロロポリエーテル残基であり、Ｒは炭素数６〜１５の２価の炭化水素基である。）
を（Ａ）成分中に含まれる２級アミノ基１モルに対して、エポキシ基の比率が１．０〜４．０モルとなる量比で含み、但し（Ａ）成分と（Ｂ）成分とは個別に包装された形態で含まれていてよい、硬化性組成物。 The present inventor has found that the above problem can be achieved by using an epoxy compound having a predetermined perfluoropolyether residue.
That is, the present invention is as follows.
(A) a fluorine-containing amino compound represented by the following formula (3);

(In the formula, Rf is a divalent perfluoropolyether residue, m is an integer of 0 to 5, and X is a divalent group represented by any of the following formulas)

(R ² and R ³ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, and R ⁴ is independently a hydrogen atom or 1 to 6 carbon atoms. Valent hydrocarbon group)
(B) A fluorine-containing epoxy obtained by polyaddition of a fluorine-containing dihydric alcohol represented by the following formula (1) and an epoxy compound represented by the following formula (2), and having an epoxy equivalent of 500 to 2500 A compound,

(Rf ″ is a divalent perfluoropolyether residue, and R is a divalent hydrocarbon group having 6 to 15 carbon atoms.)
In an amount ratio such that the ratio of the epoxy group is 1.0 to 4.0 mol with respect to 1 mol of the secondary amino group contained in the component (A), provided that the components (A) and (B) Are curable compositions that may be included in individually packaged form.

The composition of the present invention includes a solvent-resistant and flexible part in both the epoxy compound component and its curing agent component, and the cured product obtained from the composition has a hardness substantially equal to that of a conventional cured product. Nevertheless, the tensile strength and elongation at break are remarkably superior to conventional cured products.

（式中、Ｒｆは２価パーフルオロポリエーテル残基であり、ｍは０〜５の整数であり、Ｘは下記式のいずれかにて示される２価の基である。）

（Ｒ²及びＲ³は夫々、互いに独立に、置換されていてよい、炭素数１〜１０の２価炭化水素基であり、Ｒ⁴は互いに独立に、水素原子または炭素数１から６の１価炭化水素基である。） In the composition of the present invention, the component (A) has at least two secondary amino groups in one molecule represented by the following formula (3) and a divalent perfluoropolyether residue in the main chain. It is a fluorine-containing amino compound.

(In the formula, Rf is a divalent perfluoropolyether residue, m is an integer of 0 to 5, and X is a divalent group represented by any of the following formulas.)

(R ² and R ³ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, and R ⁴ is independently a hydrogen atom or 1 to 6 carbon atoms. Valent hydrocarbon group.)

In the formula (3), Rf is a divalent perfluoropolyether residue. Examples of such polyether residues broadly include divalent polymer residues having an ether linkage (—O—), such as polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol polyalkyl ether, and Those in which all hydrogen atoms of divalent residues of polyethylene glycol polyphenyl ether are substituted with fluorine atoms are included.

Preferably, Rf includes a divalent saturated perfluoropolyether residue represented by the composition formula C _h F _2h O (where h is an integer of 1 to 6, preferably 1 to 3). The saturated perfluoropolyether residue may contain a branched structure.

（ＹはＦ原子又はＣＦ₃基である） Preferably, the divalent saturated perfluoropolyether residue is represented by the following formula (i) or (ii).

(Y is F atom or CF ₃ group)

（Ｙは上で定義したとおりであり、ｍ、ｎはそれぞれｍ≧１、ｎ≧１の整数、但し、２≦ｍ＋ｎ≦２００、好ましくは２≦ｍ＋ｎ≦１００、である。）
上式は、下記のように表すこともできる。

ここで、ｋはｎ−１であり、及びｌはｍ−１である。 Preferably, Rf contains a total of 2 to 200, more preferably 2 to 100 groups represented by the above formula (i) and the above formula (ii). expressed.

(Y is as defined above, and m and n are integers of m ≧ 1 and n ≧ 1, respectively, provided that 2 ≦ m + n ≦ 200, preferably 2 ≦ m + n ≦ 100.)
The above equation can also be expressed as follows:

Here, k is n-1 and l is m-1.

（Ｙは上で定義したとおりであり、ｐ、ｑ、ｒはそれぞれｐ≧１、ｑ≧１、２≦ｐ＋ｑ≦２００、好ましくは２≦ｐ＋ｑ≦１００の整数、及び０≦ｒ≦６の整数である。）

（ｒは上述のとおり、ｓ、ｔは、それぞれｓ≧０、ｔ≧０、０≦ｓ＋ｔ≦２００、好ましくは２≦ｓ＋ｔ≦１００の整数である）

（Ｙは上述のとおり、ｕ、ｖはそれぞれ１≦ｕ≦１００、１≦ｖ≦１００の整数である）

（ｗは１≦ｗ≦１００の整数である） Rf may contain other structural units, and may be groups represented by the following (A) to (D), for example.

(Y is as defined above, and p, q and r are integers of p ≧ 1, q ≧ 1, 2 ≦ p + q ≦ 200, preferably 2 ≦ p + q ≦ 100 and 0 ≦ r ≦ 6, respectively. .)

(R is an integer of s ≧ 0, t ≧ 0, 0 ≦ s + t ≦ 200, preferably 2 ≦ s + t ≦ 100, as described above.)

(Y is an integer of 1 ≦ u ≦ 100 and 1 ≦ v ≦ 100, respectively, as described above.)

(W is an integer of 1 ≦ w ≦ 100)

Ｒｆは、上記各基の組合わせであってよく、また、上式における各数値パラメータ、例えばｎ、が所定の範囲内で異なる基の組合わせであってよい。実際上、Ｒｆは、各パラメータの平均値で特定される。 Examples of Rf represented by any of the above (A) to (D) include the following.

Rf may be a combination of the above groups, or may be a combination of groups in which each numerical parameter in the above formula, for example, n is different within a predetermined range. In practice, Rf is specified by the average value of each parameter.

In the formula (3), R ² and R ³ are each independently a divalent hydrocarbon group which may be substituted, and those having 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms are preferred. For example, methylene group, ethylene group, n-propylene group, i-propylene group, butylene group, hexamethylene group and other alkylene groups, cyclohexylene group and other cycloalkylene groups, phenylene group, tolylene group, xylylene group and naphthylene group An aryl group such as a biphenylene group, or a group in which a part of these hydrogen atoms is substituted with a halogen atom such as fluorine.

In the formula (3), R ² and the N atom is bonded directly by a single bond, in accordance with 1 to 10 carbon atoms of the R ^2, 4 to 22 membered ring, preferably a 5- to 8-membered ring, to form ing.

（ここで、Meはメチル基であり、Phはフェニル基である。） Examples of X include the following groups.

(Here, Me is a methyl group and Ph is a phenyl group.)

The amide compound may be a low-viscosity polymer having a viscosity (25 ° C., the same shall apply hereinafter) of about 100 cs to a gum or solid polymer of 100,000 cs or more. If the viscosity is less than the above lower limit, the elongation of the resulting cured product may be too small. On the other hand, if it exceeds the upper limit, handling becomes difficult. The preferred viscosity varies depending on the application. For example, a raw rubber polymer having a viscosity of 100,000 or more is suitably used for heat vulcanized rubber, and a polymer having a viscosity of about 100 to 100,000 cs is suitably used for liquid rubber. The viscosity can be adjusted by appropriately selecting each parameter of the Rf.

（Ｘ、Ｒｆ、ｍは上記と同様の意味を示す。）

上記式化合物（a）と化合物（b）の反応比率は、モル数の比率 （ａ）／（ｂ） で0.01〜0.5 ，特に0.05〜0.5とすることが好適である。また、式（３）中の繰り返し単位数ｍは、（ａ）／（ｂ）を調整することにより目的に応じた値にすることが可能であり、例えば（ａ）／（ｂ）を小さくすればｍの小さなポリマーを合成することができ、（ａ）／（ｂ）の値を大きくすればｍの大きなポリマーを合成することができる。 The amide compound can be produced by the method described in Patent Document 3. That is, a compound having an acid fluoride group at both ends represented by the following general formula (a) and a secondary diamine compound represented by the following general formula (b), if necessary, in the presence of an acid acceptor such as trimethylamine, It can be synthesized by reacting.

(X, Rf, and m have the same meaning as described above.)

The reaction ratio of the above-mentioned formula compound (a) and compound (b) is preferably 0.01 to 0.5, particularly 0.05 to 0.5 in terms of the molar ratio (a) / (b). In addition, the number m of repeating units in the formula (3) can be set to a value according to the purpose by adjusting (a) / (b). For example, (a) / (b) can be reduced. Thus, a polymer having a small m can be synthesized, and a polymer having a large m can be synthesized by increasing the value of (a) / (b).

The reaction conditions are usually 20 to 120 ° C. for 1 to 8 hours, and 40 to 100 ° C. for 2 to 5 hours. Moreover, you may use an organic solvent within the range which does not affect reaction. Examples of the organic solvent include hydrocarbon solvents such as hexane, cyclohexane, toluene and xylene, ether solvents such as diethyl ether, n-butyl ether, dioxane and tetrahydrofuran, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and ethyl acetate. Chlorinated hydrocarbon solvents such as methylene chloride, methylene chloride, chlorobenzene, and chloroform, nitrile solvents such as acetonitrile, and fluorinated solvents such as trifluorobenzene, 1,3-bistrifluoromethylbenzene, and perfluorooctane. These can be used singly or in combination of two or more as required.

（Ｒｆ”は２価のパーフロロポリエーテル残基であり、Ｒは炭素数６〜１５の２価の炭化水素基である。） The composition of the present invention is a product obtained by polyaddition of (B) a fluorine-containing divalent alcohol represented by the following formula (1) and a compound containing at least two epoxy groups represented by the following formula (2). And a fluorine-containing epoxy compound having an epoxy group having an epoxy equivalent in the range of 500 to 2500. When the epoxy group of (2) undergoes an addition reaction with the alcoholic hydroxyl group of (1), a secondary alcoholic hydroxyl group is generated. Moreover, an unreacted epoxy group remains by making (2) carry out an excess equivalent reaction with respect to (1). That is, the (B) fluorine-containing epoxy compound contains a secondary alcoholic hydroxyl group and an epoxy group. This is considered to generate a flexible cured product by reacting with the amino group of (A) and / or the epoxy group of (B).

(Rf ″ is a divalent perfluoropolyether residue, and R is a divalent hydrocarbon group having 6 to 15 carbon atoms.)

The range of the epoxy equivalent of the addition product is 500-2500, preferably 500-2000. When the epoxy equivalent exceeds the upper limit, the hardness of the cured product is insufficient, and when it is less than the lower limit, the flexibility of the cured product tends to be insufficient.

（ＹはＲｆに関し上で定義したとおりであり、ｍ´、ｎ´はそれぞれｍ´≧１、ｎ´≧１の整数、但し、２≦ｍ´＋ｎ´≦２５、好ましくは２≦ｍ´＋ｎ´≦１５、である。） Rf ″ may be the same group as Rf described above within the range where the epoxy equivalent of the addition product is 500 to 2500. Preferably, Rf ″ is a group represented by the above formula (i); It contains 2 to 25, more preferably 2 to 15 groups in total with the group represented by the above formula (ii), and is represented by the following formula, for example.

(Y is as defined above for Rf, m ′ and n ′ are integers of m ′ ≧ 1 and n ′ ≧ 1, respectively, provided that 2 ≦ m ′ + n ′ ≦ 25, preferably 2 ≦ m ′ + n '≦ 15.)

（Ｙは上述のとおりであり、ｐ、ｑ、ｒはそれぞれｐ≧１、ｑ≧１、２≦ｐ＋ｑ≦２５、好ましくは２≦ｐ＋ｑ≦１５の整数、及び０≦ｒ≦６の整数である。）

（ｒは上述のとおり、ｓ、ｔは、それぞれｓ≧０、ｔ≧０、０≦ｓ＋ｔ≦２５、好ましくは２≦ｓ＋ｔ≦１５の整数である）

（Ｙは上述のとおり、ｕ、ｖはそれぞれ１≦ｕ≦２５、１≦ｖ≦１５の整数である）

（ｗは１≦ｗ≦２５の整数である）
Rf ″ may include other structural units, and may be, for example, a group represented by any one of the following (A) to (D).

(Y is as described above, and p, q, and r are integers of p ≧ 1, q ≧ 1, 2 ≦ p + q ≦ 25, preferably 2 ≦ p + q ≦ 15 and 0 ≦ r ≦ 6, respectively. .)

(R is an integer of s ≧ 0, t ≧ 0, 0 ≦ s + t ≦ 25, preferably 2 ≦ s + t ≦ 15, as described above.)

(Y is an integer of 1 ≦ u ≦ 25 and 1 ≦ v ≦ 15, respectively, as described above.)

(W is an integer of 1 ≦ w ≦ 25)

が例示され、ｎ及びｍの範囲は付加生成物のエポキシ当量が５００〜２５００となる範囲であり、分子量が約４００〜約４０００程度である。 Preferred examples of the fluorine-containing dihydric alcohol represented by the formula (1) include

The range of n and m is a range where the epoxy equivalent of the addition product is 500 to 2500, and the molecular weight is about 400 to about 4000.

In the epoxy compound represented by the formula (2), there are preferably two epoxy groups at the terminal. Moreover, the epoxy equivalent is 50-500, Preferably it is 70-300. R includes a divalent hydrocarbon group having 6 to 15 carbon atoms, such as an alkyl group, an aryl group, and an alkaryl group. The following bisphenol A or F type epoxy group compounds are preferred.

The polyaddition of (1) fluorine-containing dihydric alcohol and (2) epoxy compound can be performed as follows. (1) 1 mol of fluorine-containing dihydric alcohol, (2) 1.5-6 mol of epoxy compound, solvent and catalyst are charged into a reactor, heated to 70-100 ° C., and stirred for 3-24 hours. After completion of the reaction, (B) can be obtained by distilling off the solvent. The epoxy equivalent of the fluorine-containing epoxy compound to be produced is adjusted by the molecular weight of the (1) fluorine-containing dihydric alcohol used at this time, (2) the epoxy equivalent of the epoxy compound, and (2) / (1) charging magnification. Is possible. The resulting (B) fluorine-containing epoxy compound is a mixture of reaction products.

  As the catalyst, triphenylphosphine, tetrabutylammonium bromide and the like are preferable, and as the solvent, toluene, xylene, 1,3-bistrifluoromethylbenzene and the like are preferable.

  The composition of the present invention is a one-component type in which the component (A) and the component (B) are mixed, or a two-component type in which the component (A) and the component (B) are separately packaged. The amount ratio of the component (A) to the component (B) is such that the ratio of the epoxy group in the component (B) to 1 mol of the secondary amino group contained in the component (A) is 1.0 to 4.0 mol. The amount is preferably 1.0 to 3.0 mol. If the amount ratio is less than the lower limit, the degree of crosslinking of the cured product may be insufficient. If the amount ratio exceeds the upper limit, the flexibility of the resulting cured product tends to decrease.

In addition to the components (A) and (B), various additives can be added to the composition of the present invention in amounts that do not impair the object of the present invention. In the case of the two-component type, an additive may be blended with each component. Examples of the additive include curing accelerators such as imidazoles and Lewis acids, carbon black such as acetylene black, fumed silica, precipitated silica, titanium dioxide, aluminum oxide, quartz powder, carbon powder, talc, bentonite and the like. Reinforcing agents, fiber fillers such as asbestos, glass fibers and organic fibers, colorants such as pigments and dyes, heat resistance improvers such as bengara and cerium oxide, rust preventives, adhesion improvements such as silane coupling agents Agents and the like. Moreover, you may mix | blend a fluorine-type solvent, for example, 1, 3-bis trifluoromethylbenzene, perfluorooctane etc. according to a use and the intended purpose.

The composition of the present invention can be prepared by mixing the above components (A) and (B), and optionally the above additives, in the case of a single agent type. In the case of the two-drug type, each component is mixed with additives as desired, packaged separately, and both components are mixed immediately before use. In addition, you may add an additive, when mixing both components. As the mixing method, a known method can be used. For example, a mixing device such as a planetary mixer, a gate mixer, or a kneader is used. After mixing (A) and (B), the mixture is allowed to stand at room temperature or heated to 50 to 100 ° C. to become an elastic body. The curing time is generally 5 to 96 hours at room temperature, and 2 to 10 hours at 80 ° C.

The elastomer obtained from the composition of the present invention is useful as an adhesive for automobile-related parts and various electric / electronic parts, and as a sealant and coating agent for sensors exposed to various gases, hot water, chemicals and the like. For example, pressure sensors, gas concentration detectors, temperature sensor adhesives, sealants or coating agents used in automobile control systems; adhesives and sealants for inkjet printer heads; rolls for laser printers and copying machines And a coating agent for a belt, a coating agent for a circuit board, and an adhesive for fixing a stepper lens of a semiconductor manufacturing apparatus.

ビスフェノールAジグリシジルエーテル 100g
トリフェニルホスフィン 1g及び、
ベンゾトリフロリド 147g
を仕込み、90℃にて21時間攪拌した。次いで、溶媒のベンゾトリフロライドをストリップにより取り除き、淡褐色のオイル状生成物245ｇ（含フッ素エポキシ化合物（B-1）とする）を得た。B-1のエポキシ当量は617g/molであった。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following, Me represents a methyl group.
1. 147g of fluorine- containing dihydric alcohol (average molecular weight 1000) with the following structure in a reaction vessel for the synthesis of fluorine-containing epoxy compound (B-1)

Bisphenol A diglycidyl ether 100g
1 g of triphenylphosphine and
Benzotrifluoride 147g
And stirred at 90 ° C. for 21 hours. Next, benzotrifluoride as a solvent was removed by stripping to obtain 245 g of a light brown oily product (referred to as fluorine-containing epoxy compound (B-1)). The epoxy equivalent of B-1 was 617 g / mol.

2. Synthesis of fluorine-containing epoxy compound (B-2) The same procedure as the synthesis of B-1 was carried out except that 92 g of bisphenol F diglycidyl ether was used instead of 100 g of bisphenol A diglycidyl ether. 243 g of a fluorine epoxy compound (B-2) was obtained. The epoxy equivalent of B-2 was 610 g / mol.

を混合し、混合物を80℃のオーブン中にて24時間加熱したところ、淡褐色のエラストマー状の硬化物が得られた。
硬化物の物性は以下のとおりであった。
硬度（Duro-A） 60
引張り強度(ＭＰ) 5.8
破断時伸び（％） 310

なお、引張強度及び破断時伸びは、ＪＩＳ Ｋ６２５１に従い測定した。 10 g of fluorine-containing epoxy compound B-1 and 30 g of fluorine-containing amino compound having the following structure

Were mixed and the mixture was heated in an oven at 80 ° C. for 24 hours to obtain a light brown elastomeric cured product.
The physical properties of the cured product were as follows.
Hardness (Duro-A) 60
Tensile strength (MP) 5.8
Elongation at break (%) 310

The tensile strength and elongation at break were measured according to JIS K6251.

を混合した。混合物を25℃にて48時間放置したところ、淡褐色のエラストマ-状の硬化物が得られた。硬化物の物性は次の通りであった。
硬度（Duro-A） 62
引張り強度(ＭＰ) 6.3
破断時伸び（％） 420 10 g of fluorine-containing epoxy compound B-1 and 25 g of fluorine-containing amino compound having the following structure

Were mixed. When the mixture was allowed to stand at 25 ° C. for 48 hours, a light brown elastomeric cured product was obtained. The physical properties of the cured product were as follows.
Hardness (Duro-A) 62
Tensile strength (MP) 6.3
Elongation at break (%) 420

を混合した。混合物を25℃にて48時間放置したところ、淡褐色のエラストマ-状の硬化物が得られた。硬化物の物性は次の通りであった。

硬度（Duro-A） 58
引張り強度(ＭＰ) 4.8
破断時伸び（％） 530 10 g of fluorine-containing epoxy compound B-2 and 25 g of fluorine-containing amino compound having the following structure

Were mixed. When the mixture was allowed to stand at 25 ° C. for 48 hours, a light brown elastomeric cured product was obtained. The physical properties of the cured product were as follows.

Hardness (Duro-A) 58
Tensile strength (MP) 4.8
Elongation at break (%) 530

Reference example 1
30 g of fluorine-containing epoxy compound B-1 and 18.4 g of both-end amino-modified silicone oil (amino group equivalent 750) were mixed and allowed to stand at 25 ° C. for 48 hours. A light brown resinous cured product was obtained. The physical properties of the cured product were as follows.

Hardness (Duro-A) 75
Tensile strength (MP) 6.8
Elongation at break (%) 70

硬度（Duro-A） 58
引張り強度(ＭＰ) 2.5
破断時伸び（％） 180 Comparative Example 1
A cured product was obtained in the same manner as in Example 1 except that 1.1 g of an epoxy compound having the following formula was used instead of the fluorine-containing epoxy compound B-1.

Hardness (Duro-A) 58
Tensile strength (MP) 2.5
Elongation at break (%) 180

Solvent swelling test The cured products prepared in Examples 1 to 3, Reference Example 1 and Comparative Example 1 were immersed in the solvents shown in the table below at 25C for 48 hours, and then the volume from the volume before immersion. From the increase rate, the swelling rate by the solvent was determined. The results are shown in the table below.

 The elastomer obtained from the composition of the present invention is useful as an adhesive for automobile-related parts and various electric / electronic parts, and as a sealant and coating agent for sensors exposed to various gases, hot water, chemicals and the like.

Claims (8)

(A) a fluorine-containing amino compound represented by the following formula (3);

(In the formula, Rf is a divalent perfluoropolyether residue, m is an integer of 0 to 5, and X is a divalent group represented by any of the following formulas)

(R ² and R ³ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, and R ⁴ is independently a hydrogen atom or 1 to 6 carbon atoms. Valent hydrocarbon group)
(B) A fluorine-containing epoxy obtained by polyaddition of a fluorine-containing dihydric alcohol represented by the following formula (1) and an epoxy compound represented by the following formula (2), and having an epoxy equivalent of 500 to 2500 A compound,

(Rf ″ is a divalent perfluoropolyether residue, and R is a divalent hydrocarbon group having 6 to 15 carbon atoms.)
In an amount ratio such that the ratio of the epoxy group is 1.0 to 4.0 mol with respect to 1 mol of the secondary amino group contained in the component (A), provided that the components (A) and (B) Are curable compositions that may be included in individually packaged form.   The component (B) is contained in an amount such that the ratio of the epoxy group is 1.0 to 3.0 mol with respect to 1 mol of the secondary amino group contained in the component (A). Curable composition. The curable composition according to claim 1 or 2, wherein the fluorine-containing dihydric alcohol represented by the formula (1) is represented by any one of the following formulas.

(N and m are arbitrary integers in the range where the molecular weight of each compound is 400 to 4000) The curable composition according to any one of claims 1 to 3, wherein the epoxy compound represented by the formula (2) is represented by any one of the following formulas.

The coating agent containing the curable composition of any one of Claims 1-4. The adhesive agent containing the curable composition of any one of Claims 1-4. The article | item provided with the hardened | cured material obtained from the curable composition of any one of Claims 1-4. The article according to claim 7, wherein the article is a lens.