JP2013082766A - Fluoro polyether-based composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluoro polyether-based composition that mainly includes a mixture of a perfluoro polyether polymer having an ester structure at both ends thereof and an inorganic filler for the preparation of a room temperature curable fluoro polyether-based rubber composition, and has reduced viscosity and improved discharging performance and mix workability.SOLUTION: The fluoro polyether-based composition includes: (a) 100 pts.mass of a straight-chain fluoro polyether compound with a number average molecular weight of 3,000 to 100,000 that includes at least two ester groups in a molecule and has a divalent perfluoro alkyether structure in a main chain; (b) 0.1-50 pts.mass of a compound with a number average molecular weight of 200 to 30,000 that includes at least one carbon acid in one molecule and has a perfolou alkyl or alkylen structure having 4 or more carbon atoms in a main chain, or a monovalent or divalent perfluoro alkyether structure; and (c) 0.5 to 300 pts.mass of an inorganic filler.

Description

  The present invention relates to a fluoropolyether composition which is cured by developing a room temperature curability by mixing with a polyfunctional amino compound to give a cured fluoropolyether rubber.

  The room temperature curable fluoropolyether rubber composition cures in a relatively short time at room temperature, and gives a cured product excellent in heat resistance, low temperature, chemical resistance, solvent resistance, oil resistance, etc. It is expected to be applied to large parts that do not enter the heating furnace, parts that cannot be heated, and sealing materials that require chemical resistance and solvent resistance.

  The present applicant previously mixed and reacted a perfluoropolyether polymer having an ester structure at both ends of the main chain with a polyfunctional amino compound in JP 2011-57809 A (Patent Document 1). It has been proposed that a rubber-like cured product can be obtained. In actual use, various inorganic fillers are blended for the purpose of improving the rubber strength and adjusting the hardness. Specifically, a component (A) mainly composed of a mixture of a perfluoropolyether polymer having an ester structure at both ends and an inorganic filler, and a component (B) mainly composed of a polyfunctional amino compound. The method of dividing and mixing these before use to finish a rubber cured product is taken.

  The viscosity of the component (A) increases as the amount of the inorganic filler is increased. At that time, there is a possibility that problems such as difficulty in discharging into the mixing container and occurrence of adverse effects such as deterioration in mixing workability with the component (B) may occur.

JP 2011-57809 A

  The present invention has been made in view of the above circumstances, and mainly comprises a mixture of a perfluoropolyether polymer having an ester structure at both ends and an inorganic filler when preparing a room temperature curable fluoropolyether rubber composition. An object of the present invention is to provide a fluoropolyether composition having reduced viscosity and improved dischargeability and mixing workability as a component.

  As a result of intensive studies to achieve the above object, the present inventors have found that a composition comprising a mixture of a perfluoropolyether polymer having an ester structure at both ends and an inorganic filler as a main component has been obtained. The fluoropolyether composition obtained by blending a carboxylate having an alkyl structure or a perfluoroalkyl ether structure is constant without increasing the viscosity of the composition even when the amount of the inorganic filler is increased. The present inventors have found that a low viscosity can be maintained, and have reached the present invention.

（式中、ｐ及びｑは１〜１５０の整数であって、かつｐとｑの和は２〜２００である。また、ｒは０〜６の整数、ｔは２又は３である。）

（式中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは上記と同じである。）

（式中、ｘは１〜２００の整数、ｙは１〜５０の整数、ｔは上記と同じである。）
〔４〕
（ｂ）成分のカルボン酸塩がカルボン酸金属塩である〔１〕〜〔３〕のいずれかに記載のフルオロポリエーテル系組成物。
〔５〕
カルボン酸金属塩の金属が、アルカリ金属及びアルカリ土類金属から選ばれるものである〔４〕記載のフルオロポリエーテル系組成物。
〔６〕
（ｂ）成分が下記式で示される化合物から選ばれるものである〔５〕記載のフルオロポリエーテル系組成物。

（式中、ｇは４〜６の整数、Ｍ、Ｍ’はＮａ又はＫである。）

（式中、ｆは１〜１６０の整数、ｓは１〜３の整数、Ｍは上記と同じである。）

（式中、ｄ及びｅはそれぞれ１〜５０の整数、Ｍは上記と同じである。）

（式中、ｍ’及びｎ’はそれぞれ０〜１００，ｍ’＋ｎ’＝０〜１６０を満足する整数、ｈ’、ｉ’、ｊ’及びｋ’はｈ’＋ｉ’＋ｊ’＋ｋ’＝２〜２００を満足する整数を示し、Ｍ、Ｍ’は上記と同じである。） Accordingly, the present invention provides the following fluoropolyether composition.
[1]
(A) a linear fluoropolyether having a number average molecular weight of 3,000 to 100,000 having at least two ester groups in one molecule and having a divalent perfluoroalkyl ether structure in the main chain Compound: 100 parts by mass
(B) Number average molecular weight containing at least one carboxylate in one molecule and having a perfluoroalkyl or alkylene structure having 4 or more carbon atoms or a monovalent or divalent perfluoroalkyl ether structure in the main chain Compound which is 200 to 30,000: 0.1 to 50 parts by mass,
(C) Inorganic filler: A fluoropolyether composition comprising 0.5 to 300 parts by mass.
[2]
The component (a) is a compound represented by the following general formula (1), [1] The fluoropolyether composition according to [1].
ROOC-Rf-COOR '(1)
(In the formula, Rf is a divalent perfluoroalkyl ether structure, and R and R ′ are the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.)
[3]
Rf is a divalent perfluoroalkyl ether group selected from the following formulas (i) to (iii): [2] The fluoropolyether composition according to [2].

(In the formula, p and q are integers of 1 to 150, and the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3.)

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)

(In the formula, x is an integer of 1 to 200, y is an integer of 1 to 50, and t is the same as above.)
[4]
(B) The fluoropolyether-type composition in any one of [1]-[3] whose carboxylate of a component is a carboxylic acid metal salt.
[5]
[4] The fluoropolyether composition according to [4], wherein the metal of the carboxylic acid metal salt is selected from alkali metals and alkaline earth metals.
[6]
(B) The fluoropolyether composition according to [5], wherein the component is selected from the compounds represented by the following formula.

(In the formula, g is an integer of 4 to 6, and M and M ′ are Na or K.)

(In the formula, f is an integer of 1 to 160, s is an integer of 1 to 3, and M is the same as above.)

(In the formula, d and e are each an integer of 1 to 50, and M is the same as above.)

(Wherein m ′ and n ′ are integers satisfying 0 to 100 and m ′ + n ′ = 0 to 160, respectively, h ′, i ′, j ′ and k ′ are h ′ + i ′ + j ′ + k ′ = 2. An integer satisfying ~ 200 is shown, and M and M ′ are the same as above.)

  The fluoropolyether composition of the present invention mainly comprises a main polymer and a filler, but by blending a compound containing a perfluoro (oxy) alkyl unit and a carboxylate in one molecule, The viscosity is reduced, and the workability during mixing and the discharge performance from the nozzle are improved.

Hereinafter, the present invention will be described in more detail.
The fluoropolyether composition of the present invention comprises (a) a linear fluoropolyether compound, (b) a carboxylate and a compound having a perfluoroalkyl structure or a perfluoroalkylether structure (hereinafter referred to as a fluorine-containing carboxylate). And (c) an inorganic filler as an essential component.

(A) Linear fluoropolyether compound The linear fluoropolyether compound of component (a) has at least two ester groups in one molecule and is a divalent perfluoroalkyl ether in the main chain The number average molecular weight having a structure is in the range of 3,000 to 100,000, and is preferably a linear fluoropolyether compound having ester groups at both ends of the molecular chain.

Examples of the component (a) include compounds represented by the following general formula (1).
ROOC-Rf-COOR '(1)
(In the formula, Rf is a divalent perfluoroalkyl ether structure, and R and R ′ are the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.)

  Here, examples of the divalent perfluoroalkyl ether structure include structures represented by the following general formulas (i), (ii), and (iii).

（式中、ｐ及びｑは１〜１５０の整数であって、かつｐとｑの和は２〜２００である。また、ｒは０〜６の整数、ｔは２又は３である。）

(In the formula, p and q are integers of 1 to 150, and the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3.)

（式中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは上記と同じである。）

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)

（式中、ｘは１〜２００の整数、ｙは１〜５０の整数、ｔは上記と同じである。）

(In the formula, x is an integer of 1 to 200, y is an integer of 1 to 50, and t is the same as above.)

  As the unsubstituted or substituted monovalent hydrocarbon groups R and R ′ in the ester group in the linear fluoropolyether compound of component (a), those having 1 to 8 carbon atoms, particularly those having 1 to 3 carbon atoms, may be used. Preferably, for example, alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, vinyl group, allyl group Alkenyl groups such as groups, and those in which some of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, iodine, etc. are particularly preferred alkyl groups having 1 to 3 carbon atoms. .

  The linear fluoropolyether compound (a) has a polystyrene-reduced number average molecular weight of 3,000 to 100,000 by gel permeation chromatography (GPC) using hydrochlorofluorocarbon (HCFC) -225 as a developing solvent. It is desirable that it is 3,000 to 50,000. When the number average molecular weight is less than 3,000, the mechanical strength is inferior, and when the number average molecular weight exceeds 100,000, the workability is inferior.

Here, the number average molecular weight referred to in the present invention refers to the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) measured under the following conditions (hereinafter the same).
[Measurement condition]
Developing solvent: Hydrochlorofluorocarbon (HCFC) -225
Flow rate: 1 mL / min.
Detector: Evaporative light scattering detector
Column: TSKgel Multipore HXL-M manufactured by Tosoh Corporation
7.8 mmφ × 30 cm 2 column temperature used: 35 ° C.
Sample injection amount: 100 μL (HCFC-225 solution with a concentration of 0.1% by mass)

  Specific examples of the linear fluoropolyether compound represented by the general formula (1) include those represented by the following formula. These compounds may be used alone or in combination of two or more. You may use together.

（式中、ｍ及びｎはそれぞれ０〜６００、ｍ＋ｎ＝２０〜６００を満足する整数、ｈ、ｉ、ｊ及びｋはｈ＋ｉ＋ｊ＋ｋ＝２０〜１，０００を満足する整数を示す。）

(In the formula, m and n are integers satisfying 0 to 600 and m + n = 20 to 600, respectively, h, i, j and k are integers satisfying h + i + j + k = 20 to 1,000.)

(B) Fluorinated carboxylate (b) The fluorinated carboxylate of component (b) contains at least one, preferably 1-2 carboxylates per molecule, and has 4 or more carbon atoms in the main chain. A compound having a number average molecular weight of 200 to 30,000 having a perfluoroalkyl or alkylene structure having 4 to 500 carbon atoms or a monovalent or divalent perfluoroalkyl ether structure. In this composition, the carboxylate portion is oriented or bonded to the surface of the inorganic filler in the composition, and the fluorine group component faces outward, so that the surface of the filler is covered with the fluorine group. To do. Thereby, the affinity between the polymer of the component (a) and the filler is improved, the dispersibility of the filler is improved, and the fluidity of the composition is also improved. As a result, the viscosity of the composition is lowered. .

  Examples of compounds that form carboxylates include organic compounds such as ammonia, primary amino compounds, secondary amino compounds, and tertiary amino compounds, and inorganic compounds such as alkali metals and amphoteric metals. Considering the ease and stability of the salt, the salt with the inorganic compound is good, and it is preferably a salt with a metal (carboxylic acid metal salt). Among these metals, lithium, sodium, potassium, Alkali metals such as rubidium and cesium and alkaline earth metals such as magnesium, calcium, strontium and barium are preferred, and sodium and potassium are most preferred.

  As the fluorine group, a perfluoro group having 4 or more carbon atoms, preferably 4 to 500 carbon atoms in the main chain (that is, a perfluoroalkyl structure or a perfluoroalkyl ether) in consideration of affinity with the component (a) Structure). When the number of carbon atoms is less than 4, the properties as a perfluoro compound are insufficient, and the affinity with the component (a) is poor.

Examples of the component (b) include compounds represented by the following general formulas (2) and (3).
MOOC-Rf ¹ -COOM '(2)
Rf ² -COOM (3)
(In the formula, Rf ¹ is a perfluoroalkylene structure or a divalent perfluoroalkyl ether structure having 4 or more carbon atoms, and Rf ² is a perfluoroalkyl structure or a monovalent perfluoroalkyl ether structure having 4 or more carbon atoms. And M and M ′ are Na or K.)

  Here, examples of the perfluoroalkyl or alkylene structure having 4 or more carbon atoms or the monovalent or divalent perfluoroalkyl ether structure include structures represented by the following general formulas (i) to (vii).

（式中、ｇは４〜６の整数である。）

(In the formula, g is an integer of 4 to 6.)

（式中、ｆは１〜１６０、好ましくは２〜１００の整数、ｓは１〜３の整数である。）

(In the formula, f is an integer of 1 to 160, preferably 2 to 100, and s is an integer of 1 to 3.)

（式中、ｄ及びｅはそれぞれ１〜５０の整数である。）

(In the formula, d and e are each an integer of 1 to 50.)

（式中、ｐ及びｑは１〜１５０の整数であって、かつｐとｑの和は２〜２００である。また、ｒは０〜６の整数、ｔは２又は３である。）

(In the formula, p and q are integers of 1 to 150, and the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3.)

（式中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは上記と同じである。）

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)

（式中、ｘは１〜２００の整数、ｙは１〜５０の整数、ｔは上記と同じである。）

(In the formula, x is an integer of 1 to 200, y is an integer of 1 to 50, and t is the same as above.)

  The compound (b) has a polystyrene-reduced number average molecular weight of 200 to 30,000 by gel permeation chromatography (GPC) using hydrochlorofluorocarbon (HCFC) -225 as a developing solvent, and 500 to 20,000. It is desirable that If the number average molecular weight is less than 200, the properties as a perfluoro compound are insufficient, the affinity with the component (a) is poor, and if the number average molecular weight exceeds 30,000, the component (b) itself has a high viscosity, There is a risk that workability may be hindered.

（式中、ｇは４〜６の整数である。） Examples of such compounds of component (b) include, but are not limited to, those shown below. In the following examples, M and M ′ are Na or K.

(In the formula, g is an integer of 4 to 6.)

（式中、ｆは１〜１６０、好ましくは２〜１００の整数、ｓは１〜３の整数である。）

(In the formula, f is an integer of 1 to 160, preferably 2 to 100, and s is an integer of 1 to 3.)

（式中、ｄ及びｅはそれぞれ１〜５０の整数である。）

(In the formula, d and e are each an integer of 1 to 50.)

（式中、ｍ’及びｎ’はそれぞれ０〜１００，ｍ’＋ｎ’＝０〜１６０を満足する整数、ｈ’、ｉ’、ｊ’及びｋ’はｈ’＋ｉ’＋ｊ’＋ｋ’＝２〜２００を満足する整数を示す。）
これらの化合物は１種単独で使用してもよいし、２種以上を併用してもよい。

(Wherein m ′ and n ′ are integers satisfying 0 to 100 and m ′ + n ′ = 0 to 160, respectively, h ′, i ′, j ′ and k ′ are h ′ + i ′ + j ′ + k ′ = 2. An integer satisfying -200 is shown.)
These compounds may be used individually by 1 type, and may use 2 or more types together.

  Component (b) is added in an amount of 0.1 to 50 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component (a). When the amount is less than 0.1 parts by mass, the effect of decreasing the viscosity is hardly exhibited. When the amount is more than 50 parts by mass, the rubber strength of the cured product obtained after reacting with the polyfunctional amino compound is affected.

(C) Inorganic filler (c) The inorganic filler of a component is mix | blended for the objectives, such as provision of the rubber strength after hardening, and adjustment of hardness. Such inorganic fillers include natural silica, synthetic silica produced by wet or dry methods, kaolin, mica, talc, clay, montmorillonite, zeolite, natural silicate, glass powder, glass fiber, calcium silicate, Silicates such as aluminum silicate, metal oxides such as alumina, titanium oxide, magnesium oxide and zinc oxide, metal hydroxides such as calcium hydroxide, aluminum hydroxide and magnesium hydroxide, light calcium carbonate, heavy carbonate Examples thereof include calcium, various surface-treated calcium carbonates, metal carbonates such as magnesium carbonate, metal sulfates such as barium sulfate, magnesium sulfate, and calcium sulfate, metal powders such as aluminum and bronze, and carbon black.

  The particle size of the inorganic filler is not limited, but the primary particle size is preferably 50 μm or less, and more preferably 10 μm or less. If the particle size is too large, there is a possibility that problems such as poor dispersibility in the component (a) and sedimentation of the quality filler may occur. The primary particle size of the inorganic filler is preferably 1 nm or more. The particle size can be measured by a known method such as a dynamic light scattering method, a laser diffraction / scattering method, or an image imaging method.

  The compounding amount of the inorganic filler may be an appropriate amount depending on the purpose, but is 0.5 to 300 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of component (a). . If the amount of the inorganic filler is too small, sufficient mechanical strength and hardness cannot be obtained after curing, and if too large, sufficient elongation characteristics cannot be obtained after curing.

Other components In the composition of the present invention, various known additives can be blended by a known method, if necessary, within a range not impairing the effects of the present invention.
Specific examples include iron oxide, cerium oxide, and carbon black as pigments, colorants, dyes, antioxidants, and oil-like compounds partially or wholly fluorine-modified as viscosity modifiers. In addition, the addition amount of these arbitrary components can be made into a normal amount in the range which does not inhibit the effect of this invention.

The composition of this invention can be prepared by mixing said each component uniformly.
The composition of the present invention thus obtained has a viscosity at 23 ° C. of 1 to 500 Pa · s, particularly about 5 to 300 Pa · s, measured at a speed of 10 rpm using a Brookfield type rotational viscometer. It has a low viscosity.

Method of Use The composition of the present invention is preferably mixed with a polyfunctional amino compound by a known method and used as a room temperature curable fluoropolyether rubber composition. A hardened | cured material can be obtained by leaving it to stand at room temperature (for example, 5-35 degreeC) for 3 days or more after mixing.

  Here, the polyfunctional amino compound to be mixed with the composition of the present invention acts as a cross-linking agent and a chain extender of the component (a), and has an amino group, particularly a primary amino group, in one molecule. It is preferable to use an amino group-containing siloxane polymer containing at least 3 or more.

  In addition, in order to improve the dispersibility of the amino group-containing siloxane polymer in the component (a), one or more fluorine-modified groups may be introduced into the amino group as required. Examples of the fluorine-modified group herein include a monovalent perfluoroalkyl group and a monovalent perfluoroalkyl ether group, and the molecular structure may be either a chain or a branched structure. Representative examples thereof include groups represented by the following general formula, but are not limited thereto.

（式中、ｇ１は１〜６、好ましくは４〜６の整数である。）

(In the formula, g1 is an integer of 1 to 6, preferably 4 to 6.)

（式中、ｆ１は２〜２００、好ましくは２〜１００の整数、ｓ１は１〜３の整数である。）

(In the formula, f1 is an integer of 2 to 200, preferably 2 to 100, and s1 is an integer of 1 to 3.)

（式中、ｄ１及びｅ１はそれぞれ１〜５０の整数である。）

(In the formula, d1 and e1 are each an integer of 1 to 50.)

  These perfluoroalkyl groups and perfluoroalkyl ether groups can be introduced, for example, into the following fluorine-containing terminal ester compounds and introduced into the amino groups of the amino group-containing siloxane polymer by a dealcoholization reaction or the like according to JP-A-7-18079. it can. However, the terminal ester compound is not limited to the following.

（式中、ｇ１は１〜６、好ましくは４〜６の整数である。）

(In the formula, g1 is an integer of 1 to 6, preferably 4 to 6.)

（式中、ｆ１は２〜２００、好ましくは２〜１００の整数、ｓ１は１〜３の整数である。）

(In the formula, f1 is an integer of 2 to 200, preferably 2 to 100, and s1 is an integer of 1 to 3.)

（但し、ｄ１及びｅ１はそれぞれ１〜５０の整数である。）

(However, d1 and e1 are each an integer of 1 to 50.)

The amino group of the amino group-containing siloxane polymer is preferably a primary amino group (—NH ₂ ), and the number of amino groups in the molecule, particularly the number of primary amino groups in the siloxane polymer is not particularly limited. ~ 100, preferably 3-50, especially about 4-20.

  Such an amino group-containing siloxane polymer may have, for example, a linear, cyclic, or branched siloxane structure, and the number of silicon atoms in the molecule is usually 3 to 200, Preferably, it may be about 4 to 100. Examples of such amino group-containing siloxane polymers include the following compounds.

（式中、ｎ１は３〜５０、好ましくは３〜３０の整数である。）

(In the formula, n1 is an integer of 3 to 50, preferably 3 to 30.)

（式中、ｎ１は３〜５０、好ましくは３〜３０の整数である。）

(In the formula, n1 is an integer of 3 to 50, preferably 3 to 30.)

（式中、ａ１は３〜５０、好ましくは３〜２０の整数、ｂ１は１〜５０、好ましくは１〜１０の整数、ａ１＋ｂ１＝４〜１００、ｃ１は０〜１００、好ましくは１〜３０の整数である。）

(Wherein, a1 is an integer of 3-50, preferably 3-20, b1 is an integer of 1-50, preferably 1-10, a1 + b1 = 4-100, c1 is 0-100, preferably 1-30. (It is an integer.)

（式中、ａ１は３〜５０、好ましくは３〜２０の整数、ｂ１は１〜５０、好ましくは１〜１０の整数、ａ１＋ｂ１＝４〜１００、ｎ１は１〜１０、好ましくは１〜６の整数である。）

(Wherein, a1 is an integer of 3-50, preferably 3-20, b1 is an integer of 1-50, preferably 1-10, a1 + b1 = 4-100, n1 is 1-10, preferably 1-6. (It is an integer.)

（式中、ａ１は３〜５０、好ましくは３〜２０の整数、ｂ１は１〜５０、好ましくは１〜１０の整数、ｄ１は１〜５０、好ましくは１〜１０の整数、ａ１＋ｂ１＋ｄ１＝４〜１００、ｃ２は０〜１０、好ましくは１〜５の整数、ｅ１は１１〜１００、好ましくは２０〜５０の整数である。）

(Wherein a1 is an integer of 3 to 50, preferably 3 to 20, b1 is an integer of 1 to 50, preferably 1 to 10, d1 is an integer of 1 to 50, preferably 1 to 10, a1 + b1 + d1 = 4 to 100, c2 is an integer of 0 to 10, preferably 1 to 5, and e1 is an integer of 11 to 100, preferably 20 to 50.)

  This amino group-containing siloxane polymer may be used alone or in combination of two or more.

  The compounding amount of the amino group-containing siloxane polymer that can be mixed with the fluoropolyether composition of the present invention is usually contained in the component (a) and component (b), for example, methyl ester group, ethyl ester group, propyl The ratio of the total amount of amino groups (particularly primary amino groups) of the present amino group-containing siloxane polymer to the total amount of ester groups such as ester groups is preferably 1.0 to 5.0 (molar ratio), more preferably Is preferably in an amount of 2.0 to 4.0 (molar ratio). If the molar ratio is less than 1.0, the degree of crosslinking may be inadequate and the mechanical strength may be inferior. May not be obtained.

Use The cured | curing material obtained using the composition of this invention can be utilized for various uses. In other words, it has a high fluorine content, so it has excellent solvent resistance and chemical resistance, low moisture permeability, and low surface energy, so it has excellent releasability and water repellency, thus requiring oil resistance. Rubber parts for automobiles, specifically automobile diaphragms, valves, seals, etc .; rubber parts for chemical plants, specifically pump diaphragms, valves, hoses, packings, oil seals, Sealing materials such as gaskets and tank pipe repair sealing materials; rubber parts for inkjet printers; rubber parts for semiconductor manufacturing lines, specifically sealing materials for diaphragms, valves, packings, gaskets, etc. for equipment that comes into contact with chemicals, etc. Valves that require low friction and wear resistance, etc. Rubber parts for analysis and physics and chemistry equipment, specifically diaphragms for pumps, valves, seal parts (packaging) Rubber parts for medical equipment, specifically pumps, valves, joints, etc .; tent film materials; sealants; molded parts; extruded parts; coating materials; copier roll materials; Useful for potting materials; sealing materials for fuel cells; sealing materials for machine tools; laminated rubber cloths.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. The number average molecular weight (or number average degree of polymerization) was measured by gel permeation chromatography (GPC) analysis using Asahi Clin AK-225 (Asahi Glass Co., Ltd., Hydrochlorofluorocarbon (HCFC) -225) as a developing solvent. Is.

[Example 1]
100 parts by mass of polymer A (viscosity 7.8 Pa · s, number average molecular weight 15,700) represented by the following formula (4), colloidal calcium carbonate surface-treated with a fatty acid on the filler (average particle size; 03 to 0.06 μm, product name Carlex 300: manufactured by Maruo Calcium Co., Ltd., trade name) 42 parts by mass, compound B having a carboxylic acid sodium salt represented by the following formula (5): 5 parts by mass of a planetary mixer The mixture was kneaded for 1 hour. Subsequently, dispersion was promoted with three rolls to produce a base compound, and the viscosity at 23 ° C. was measured at a speed of 10 rpm using a Brookfield type rotational viscometer.

（ｍ＋ｎ≒９０（数平均重合度）） [Example 2]
100 parts by mass of polymer A represented by the formula (4) (viscosity 7.8 Pa · s, number average molecular weight 15,700), colloidal calcium carbonate surface-treated with fatty acid (average particle size; 03 to 0.06 μm, product name Carlex 300: manufactured by Maruo Calcium Co., Ltd., trade name) 42 parts by mass, compound C having a carboxylic acid sodium salt represented by the following formula (6): 3 parts by mass of a planetary mixer The mixture was kneaded for 1 hour. Subsequently, dispersion was promoted with three rolls to produce a base compound, and the viscosity at 23 ° C. was measured at a speed of 10 rpm using a Brookfield type rotational viscometer.

(M + n≈90 (number average degree of polymerization))

[Example 3]
100 parts by mass of polymer A (viscosity 7.8 Pa · s, number average molecular weight 15,700) represented by the formula (4), fumed silica (specific surface area 180 m ²⁾ surface-treated with hexamethyldisilazane as a filler / G) 10 parts by mass and 3 parts by mass of Compound B having a carboxylic acid sodium salt represented by the above formula (5) were added to a planetary mixer and kneaded for 1 hour. Subsequently, dispersion was promoted with three rolls to produce a base compound, and the viscosity at 23 ° C. was measured at a speed of 10 rpm using a Brookfield type rotational viscometer.

[Comparative Example 1]
In Example 1, a base compound was produced in the same procedure without blending the fluorine-containing carboxylate (Compound B), and the viscosity at 23 ° C. was measured at a speed of 10 rpm using a Brookfield rotary viscometer. .

[Comparative Example 2]
In Example 3, a base compound was produced in the same procedure without blending the fluorine-containing carboxylate (Compound B), and the viscosity at 23 ° C. was measured at a speed of 10 rpm using a Brookfield rotary viscometer. .

  Examples 1 to 3 are cases where a fluorine-containing carboxylate was blended, and Comparative Examples 1 and 2 were cases where a fluorine-containing carboxylate was not blended. From the results of Table 1 above, it can be seen that when fluorine-containing carboxylates such as Compound B and Compound C are blended, the effect of reducing the viscosity is great.

[Reference Example 1]
Fluorine-modified amino group-containing siloxane polymer represented by the following formula (7) (viscosity 1,000 Pa · s, number average molecular weight 16,000) 69.0 parts by mass, and calcium carbonate (product name Whiten SSB red: Shiraishi calcium (stock) ), Product name) 12.0 parts by mass were charged into a planetary mixer, kneaded for 15 minutes, and then mixed under reduced pressure (-65 to -75 cmHg) at room temperature for 30 minutes. Thereafter, 40.0 parts by mass of an oily fluoropolymer represented by the following formula (8) as a viscosity modifier is added to the obtained compound, kneaded for 15 minutes with a planetary mixer, and then for 30 minutes at room temperature. Mixing under reduced pressure (−65 to −75 cmHg) was performed to produce a crosslinker compound.

  147 parts by mass of the base compound obtained in Example 1 and 121 parts by mass of the above-mentioned crosslinking agent compound were mixed, degassed under reduced pressure, poured into a sheet-like mold having a thickness of 2 mm, and left at room temperature of 23 ° C. . When observed 3 days after standing, it was confirmed to be cured in a rubbery form. When the rubber properties were measured according to JIS K6251 and JIS K6253, the hardness (Type-A) = 34, the tensile strength = 1.1 MPa, and the elongation at break = 230%.

Claims (6)

(A) a linear fluoropolyether having a number average molecular weight of 3,000 to 100,000 having at least two ester groups in one molecule and having a divalent perfluoroalkyl ether structure in the main chain Compound: 100 parts by mass
(B) Number average molecular weight containing at least one carboxylate in one molecule and having a perfluoroalkyl or alkylene structure having 4 or more carbon atoms or a monovalent or divalent perfluoroalkyl ether structure in the main chain Compound which is 200 to 30,000: 0.1 to 50 parts by mass,
(C) Inorganic filler: A fluoropolyether composition comprising 0.5 to 300 parts by mass. The fluoropolyether composition according to claim 1, wherein the component (a) is a compound represented by the following general formula (1).
ROOC-Rf-COOR '(1)
(In the formula, Rf is a divalent perfluoroalkyl ether structure, and R and R ′ are the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.) The fluoropolyether composition according to claim 2, wherein Rf is a divalent perfluoroalkyl ether group selected from the following formulas (i) to (iii).

(In the formula, p and q are integers of 1 to 150, and the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3.)

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)

(In the formula, x is an integer of 1 to 200, y is an integer of 1 to 50, and t is the same as above.)   The fluoropolyether composition according to any one of claims 1 to 3, wherein the carboxylate (b) is a carboxylic acid metal salt.   The fluoropolyether composition according to claim 4, wherein the metal of the carboxylic acid metal salt is selected from alkali metals and alkaline earth metals. 6. The fluoropolyether composition according to claim 5, wherein the component (b) is selected from the compounds represented by the following formula.

(In the formula, g is an integer of 4 to 6, and M and M ′ are Na or K.)

(In the formula, f is an integer of 1 to 160, s is an integer of 1 to 3, and M is the same as above.)

(In the formula, d and e are each an integer of 1 to 50, and M is the same as above.)

(Wherein m ′ and n ′ are integers satisfying 0 to 100 and m ′ + n ′ = 0 to 160, respectively, h ′, i ′, j ′ and k ′ are h ′ + i ′ + j ′ + k ′ = 2. An integer satisfying ~ 200 is shown, and M and M ′ are the same as above.)