Lithium ion battery

Abstract

To provide a lithium ion battery having a cured product of a fluoropolyether-based curable composition which gives a cured product having durability against hydrofluoric acid and an electrolytic solution for a lithium ion battery, having no uncured part due to low compatibility between constituent components, and having good releasability.SOLUTION: (A) a perfluoropolyether compound having at least two alkenyl groups per molecule, (B) a polyorganosiloxane compound containing no siloxane bond per molecule, represented by the general formula (1): A battery comprising a cured product of a fluoropolyether-based curable composition comprising a fluorinated organohydrogensilane compound having at least two hydrosilyl groups, wherein Rf is a monovalent perfluoropolyether group, A is a divalent organic group, R is a monovalent hydrocarbon group, x is 1 to 3, B is a monovalent organic group having a diorganohydrosilyl group and forming a silalkylene structure with the silicon atom to which it is attached, and y is 1 or 2, and (C) a platinum group metal catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a lithium ion battery having a cured product of a fluoropolyether-based curable composition that has durability against hydrofluoric acid and lithium ion battery electrolytes, is free from uncured areas due to low compatibility between the constituent components, and provides a cured product with good mold releasability. [Background technology]

[0002] Fluoropolyether-based curable compositions utilizing the addition reaction between alkenyl groups and hydrosilyl groups are known. For example, proposed curable compositions include a fluoropolyether compound (hereinafter also referred to as "base oil") having two or more alkenyl groups per molecule and a perfluoropolyether structure in the main chain, a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms per molecule, and a platinum group metal compound (Patent Document 1: JP 8-199070 A, Patent Document 2: JP 2011-201940 A). Furthermore, proposed compositions include a third component (adhesion improver) that is an organopolysiloxane having hydrosilyl groups and epoxy and / or trialkoxysilyl groups, thereby imparting self-adhesion to the composition (Patent Document 3: JP 9-95615 A, Patent Document 4: JP 2011-219692 A). The composition can be cured by heating for a short time, and the resulting cured product (fluoropolyether-based cured product) has excellent solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, electrical properties, etc., and is therefore used in various industrial fields where these properties are required.

[0003] Fluoropolyether-based curable compositions containing fluorine-containing organohydrogensiloxanes having two or more hydrogen atoms directly bonded to silicon atoms per molecule contain acid-labile siloxane bonds and are therefore unable to exhibit sufficient performance in applications requiring high levels of acid resistance. In particular, they have low resistance to hydrofluoric acid, making them unsuitable for applications such as semiconductor manufacturing equipment components. In response to this, it has been proposed to improve the acid resistance of fluoropolyether-based cured materials by using fluorine-containing organohydrogensilane compounds that do not contain siloxane bonds and have two or more hydrogen atoms directly bonded to silicon atoms per molecule instead of the fluorine-containing organohydrogensiloxanes (Patent Document 5: JP 2002-012769 A).

[0004] On the other hand, the fluorine-containing organohydrogensilane compound tends to have a large proportion of non-fluorinated organic structures in the entire molecule. This is largely due to the convenience of synthesizing the fluorine-containing organohydrogensilane compound. In this case, the short-chain perfluoroalkylene group has poor compatibility with base oils. Due to these tendencies, when a fluorine-containing organohydrogensilane compound is added to a fluoropolyether-based curable composition, the fluoropolyether-based curable composition may become cloudy and have an increased viscosity. Furthermore, the surface of the fluoropolyether-based cured product obtained from the fluoropolyether-based curable composition may also have scattered oily uncured portions. The scattered uncured portions often impair the mold releasability of the fluoropolyether-based cured product, which is undesirable in the manufacturing process of an article containing the cured product, as the cured product may not peel off from parts in the manufacturing equipment, preventing smooth production.

[0005] In recent years, growing concern about environmental issues has led to active worldwide development of products using lithium-ion batteries. However, it has been found that fluoropolyether-based curable compositions containing fluorine-containing organohydrogensiloxanes having two or more hydrogen atoms directly bonded to silicon atoms per molecule and their cured products have low durability against electrolyte solutions for lithium-ion batteries, making their application difficult. Furthermore, as for fluoropolyether-based curable compositions containing fluorine-containing organohydrogensilane compounds having no siloxane bonds and two or more hydrogen atoms directly bonded to silicon atoms per molecule instead of the fluorine-containing organohydrogensiloxanes, there has been no knowledge regarding their durability against electrolyte solutions for lithium-ion batteries, and it has been unclear whether they can be applied to this application. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 8-199070 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-201940 [Patent Document 3] Japanese Patent Application Publication No. 9-95615 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-219692 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-012769 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lithium ion battery having a cured product of a fluoropolyether-based curable composition that has durability against hydrofluoric acid and an electrolyte solution for lithium ion batteries, is free from uncured areas due to low compatibility between the constituent components, and provides a cured product with good mold releasability. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems and have found that when a fluorine-containing organohydrogensilane compound obtained by introducing a compound having a monovalent perfluoropolyether group and an alkenyl group into an organohydrogensilane compound having three or more hydrosilyl groups of a specific structure is used as a curing agent for a fluoropolyether-based curable composition, it exhibits high compatibility with the perfluoropolyether compound having an alkenyl group as a base oil.Furthermore, they have found that the cured product obtained by curing the fluoropolyether-based curable composition obtained by adding the fluorine-containing organohydrogensilane compound exhibits durability against hydrofluoric acid and lithium-ion battery electrolyte, has no uncured areas on the surface, and has good mold releasability, thereby completing the present invention.

[0009] Accordingly, the present invention provides the following lithium ion battery: 1. (A) a perfluoropolyether compound having two or more alkenyl groups in one molecule, (B) a fluorine-containing organohydrogensilane compound represented by the following general formula (1), which does not contain a siloxane bond in the molecule and has two or more hydrosilyl groups, and [ka] (In the formula, Rf is a monovalent perfluoropolyether group; A is a divalent organic group having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and silicon atoms; R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; x is an integer from 1 to 3; B is independently a monovalent organic group which has one or more diorganohydrosilyl groups and forms a silalkylene structure with the silicon atom to which it is linked; when x is 1, B has two or more diorganohydrosilyl groups; and y is 1 or 2.) (C)Platinum group metal catalyst A lithium ion battery comprising a cured product of a fluoropolyether-based curable composition comprising: 2. 2. The lithium ion battery according to 1, wherein the base oil in the fluoropolyether-based curable composition comprises component (A). 3. 2. The lithium ion battery according to 1, wherein the fluoropolyether-based curable composition does not contain a reinforcing filler. 4. 2. The lithium ion battery according to 1, wherein the fluoropolyether-based curable composition does not contain an organohydrogenpolysiloxane compound having, in one molecule, at least one hydrogen atom bonded to a silicon atom and at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. 5. 2. The lithium ion battery according to 1, wherein the component (A) in the fluoropolyether-based curable composition is a perfluoropolyether compound represented by the following general formula (2): [ka] [In the formula, A 1 are independently a divalent organic group having 1 to 20 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, and B 1 is a carbon atom or a silicon atom, and X is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least two of X are alkenyl groups having 2 to 8 carbon atoms, and when X is a hydrogen atom, the B to which it is bonded 1 is a carbon atom. Rf 1 is a divalent perfluoropolyether group. 6. 2. The lithium ion battery according to 1, wherein in the component (B) in the fluoropolyether-based curable composition, Rf in the general formula (1) is a group represented by the following general formula (5): [ka] (In the formula, D is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms; a, b, c, and d each independently represent an integer of 0 to 100, 2≦a+b+c+d≦100; and e is an integer of 1 to 3. The repeating units shown in the parentheses may be bonded randomly, and these units may be linear or branched.) 7. 2. The lithium ion battery according to 1, wherein in component (B) of the fluoropolyether-based curable composition, A in the general formula (1) is selected from alkylene groups having 1 to 12 carbon atoms, alkylene groups containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups are bonded to each other via a diorganosilylene group, divalent groups in which an alkylene group and an arylene group are bonded to each other via a diorganosilylene group, and divalent groups in which these groups further have at least one bond selected from an ether-bonded oxygen atom, a secondary amino group, a tertiary amino group, and an amide bond. 8. 2. The lithium ion battery according to 1, wherein in the component (B) in the fluoropolyether-based curable composition, A in the general formula (1) is any one of the groups represented by the following general formulas (6) to (9). [ka] (In the formula, X 0 is a hydrogen atom, a methyl group, or an ethyl group, and X 1 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and X 2 is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, R' is independently a methyl group or an ethyl group, f is an integer of 1 to 6, and t is 0 or 1. Note that the bond marked with * indicates that it is bonded to the Si atom in the above general formula (1), and the bond without a mark indicates that it is bonded to Rf. 9. 2. The lithium ion battery according to 1, wherein in the component (B) in the fluoropolyether-based curable composition, R in the general formula (1) is any one of a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, and a phenyl group. 10. 2. The lithium ion battery according to 1, wherein in the component (B) in the fluoropolyether-based curable composition, there are two or more consecutive silalkylene structures in the molecular chain between Rf in the general formula (1) and the diorganohydrosilyl group in B. 11. 2. The lithium ion battery according to 1, wherein in the component (B) in the fluoropolyether-based curable composition, B in the general formula (1) is a group represented by the following general formula (10): [ka] [In the formula, p is an integer of 1 to 6, q is an integer of 0 to 6, r is an integer of 1 to 3, R is the same as above, and E is a hydrogen atom or a group represented by the following formula: [ka] (wherein R is the same as above, p' is an integer of 1 to 6, and q' is an integer of 0 to 6) (provided that when E is a hydrogen atom, r is 1). The repeating units shown in parentheses with p, q or p', q' above may be bonded randomly.) [Effects of the Invention]

[0010] The fluoropolyether-based curable composition of the present invention contains a fluorine-containing organohydrogensilane compound of a specific structure that exhibits high compatibility with the base oil, component (A), and therefore does not cause the fluoropolyether-based curable composition to become cloudy or thicken. Furthermore, by curing the composition, a fluoropolyether-based cured product can be obtained that is resistant to hydrofluoric acid and lithium-ion battery electrolytes and is free of scattered oily uncured portions. Furthermore, the fluoropolyether-based curable composition has excellent heat resistance, chemical resistance, and solvent resistance comparable to those of the fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions described in Patent Documents 1 to 5. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will now be described in further detail. [Component (A)] The perfluoropolyether compound of component (A) used in the fluoropolyether-based curable composition of the present invention has at least two alkenyl groups in one molecule, and preferably has a divalent perfluoropolyether structure in the main chain as represented by general formula (2) described below, and acts as the main agent (base oil) in the fluoropolyether-based curable composition of the present invention.

[0012] In the present invention, the degree of polymerization (or molecular weight) of a polyfluoro compound, which reflects the number of repetitions of the perfluorooxyalkylene units constituting the perfluoropolyether structure of the main chain, can be determined, for example, as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. The number average degree of polymerization (or number average molecular weight) of a perfluoropolyether compound, which will be described later, can be determined as follows: 19 It can also be calculated from F-NMR (the same applies below).

[0013] The component (A) is preferably a perfluoropolyether compound having a structure represented by the following general formula (2). [ka] [In the formula, A 1 are independently a divalent organic group having 1 to 20 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, and B 1 is a carbon atom or a silicon atom, and X is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least two of X are alkenyl groups having 2 to 8 carbon atoms, and when X is a hydrogen atom, the B to which it is bonded 1 is a carbon atom. Rf 1 is a divalent perfluoropolyether group.

[0014] In the above general formula (2), A 1are independently a divalent organic group having 1 to 20 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, and A 1 As -(CH2) f -*, -OCH2-*, -(CH2) f OCH2-*, -(CH2) f -NX 2 -CO-*, -(CH2) f -O-CO-*, or any group selected from the groups represented by the following general formulas (3) and (4). 1 and the unmarked bond is B 1 This indicates that it binds to [ka] (In the formula, X 1 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and X 2 represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, and f represents an integer of 1 to 6.

[0015] A 1 Examples of the alkyl group include -CH2-*, -CH2CH2CH2-*, -OCH2-*, -CHOCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -CH2-NH-CO-*, -CH2-N(Me)-CO-*, -CH2CH2-NH-CO-*, -(CH2)3-NH-CO-*, -(CH2)3-N(Me)-CO-*, -(CH2)3-N(Et)-CO-*, -(CH2)3-N(CH(Me)2)-CO-*, -(CH2)3-O-CO-*, and groups represented by the following general formulae (3A), (3B), (3C), (3D), (4A), (4B) and (4C), and among these, groups represented by general formula (3A) or (4A) are preferred. The bond marked with * is Rf 1 and the unmarked bond is B 1 The symbol Me denotes a methyl group, and Et denotes an ethyl group. [ka]

[0016] In the above general formula (2), B 1 is a carbon atom or a silicon atom. Furthermore, X is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least two of X are alkenyl groups having 2 to 8 carbon atoms. Of the six Xs present in the molecule (i.e., three at each end of the molecular chain), at least two (particularly, of the three Xs present at each end of the molecular chain, at least one) are alkenyl groups, and the alkenyl groups preferably have 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and have a CH2=CH- structure at the end, such as vinyl, allyl, propenyl, isopropenyl, butenyl, and hexenyl groups, with vinyl and allyl being preferred. When X is not an alkenyl group, B 1 When is a carbon atom, it becomes either a hydrogen atom or a methyl group, and when B is a 1 When the atom is a silicon atom, the structure becomes a methyl group.

[0017] In the above general formula (2), Rf 1 is a divalent perfluoropolyether group, -C g F 2g It contains a repeating unit of O- (wherein g is an integer of 1 to 6), and examples thereof include those represented by the following formula (11). -(C g F 2g O) h - (11) (In the formula, g is an integer of 1 to 6, and h is an integer of 5 to 600, preferably an integer of 10 to 400, and more preferably an integer of 30 to 200.)

[0018] Above formula-C g F 2g Examples of the repeating unit represented by O- include units represented by the following formulas. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O-

[0019] Among these, the units represented by the following formula are particularly preferred. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O-

[0020] The repeating unit in the divalent perfluoropolyether group may be composed of one of these alone or a combination of two or more of them.

[0021] The divalent perfluoropolyether group preferably contains a structure of the following formula: [ka] (wherein G is a fluorine atom or a trifluoromethyl group; p1, q1, and r1 are integers satisfying p1≧0, q1≧0, 0≦p1+q1≦200, particularly 2≦p1+q1≦150, and 0≦r1≦6 (when p1+q1=0, 1≦r1≦6); k1, a1, s1, t1, and u1 are integers satisfying 1≦k1≦3, 2≦a1≦6, 0≦s1≦100, 0≦t1≦100, 2≦s1+t1≦200, 0≦u1≦6, particularly 2≦s1+t1≦150, , 0≦u1≦4, 2≦s1+t1+u1≦150, v1 and w1 are integers that satisfy 1≦v1≦100, 1≦w1≦100, 2≦v1+w1≦200, z1 is an integer that satisfies 1≦z1≦200, k1', a1' and a1'' are integers that satisfy 1≦k1'≦3, 1≦a1'≦6, 1≦a1''≦6, a1'≠a1'', and z1' is an integer that satisfies 1≦z1'≦200. The repeating units shown in parentheses with v1 and w1 may be bonded randomly.

[0022] In the above general formula (2), Rf 1 Specific examples of the compound are those represented by the following formula: [ka] (In the formula, p1, q1, r1, v1, w1, z1, and z1' are the same as above. s1' and t1' each represent an integer of 1 to 100, and s1'+t1'=an integer of 2 to 200. t1'' is an integer of 2 to 100. Each repeating unit shown in parentheses followed by v1 and w1 may be bonded randomly.)

[0023] The perfluoropolyether compound represented by the general formula (2) includes B 1 When is a silicon atom, those represented by the following formula are particularly preferred: In the formula, Me is a methyl group, and Et is an ethyl group.

[0024] [ka] (s1' and t1' are each an integer between 1 and 100, and s1'+t1'=an integer between 2 and 200.)

[0025] [ka] (s1' and t1' are each an integer between 1 and 100, and s1'+t1'=an integer between 2 and 200.)

[0026] [ka] (s1' and t1' are each an integer between 1 and 100, and s1'+t1'=an integer between 2 and 200.)

[0027] [ka] (s1' and t1' are each an integer between 1 and 100, and s1'+t1'=an integer between 2 and 200.)

[0028] [ka] (s1' and t1' are each an integer between 1 and 100, and s1'+t1'=an integer between 2 and 200.)

[0029] The perfluoropolyether compound represented by the general formula (2) includes B 1 When is a carbon atom, the following formula is preferred: [ka] (v1 and w1 are each an integer of 1 to 100, and v1+w1=an integer of 2 to 200. Each repeating unit shown in parentheses with v1 and w1 may be bonded randomly.)

[0030] The amount of alkenyl groups contained in the perfluoropolyether compound of component (A) is preferably 0.002 to 0.3 mol / 100 g, and more preferably 0.008 to 0.12 mol / 100 g. If the amount of alkenyl groups contained in the perfluoropolyether compound is less than 0.002 mol / 100 g, the degree of crosslinking may be insufficient, which is not preferred, and if the amount of alkenyl groups exceeds 0.3 mol / 100 g, the mechanical properties of the cured product as a rubber elastomer may be impaired, which is not preferred. In the present invention, the amount of alkenyl groups is 1 It can be measured by H-NMR (the same applies to the examples).

[0031] The viscosity (23°C) of the perfluoropolyether compound of component (A) is preferably in the range of 40 to 100,000 mPa·s, more preferably 50 to 50,000 mPa·s, and even more preferably 60 to 20,000 mPa·s, because the cured product of the fluoropolyether-based curable composition of the present invention has suitable physical properties when used for sealing, potting, coating, impregnation, etc. Within this viscosity range, the most appropriate viscosity can be selected depending on the application. In the present invention, the viscosity (23°C) can be measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.) (the same applies hereinafter).

[0032] As the component (A), these perfluoropolyether compounds can be used either individually or in combination of two or more.

[0033] [(B) Component] The component (B) used in the fluoropolyether-based curable composition of the present invention is a fluorine-containing organohydrogensilane compound represented by the following general formula (1) and having two or more hydrosilyl groups. Specifically, it is a compound having two or more hydrosilyl groups, in which all of the connections between silicon atoms are formed by a silalkylene structure (note that the alkylene groups in the silalkylene structure may be fluorine-substituted alkylene groups that are partially substituted with fluorine), and does not contain a siloxane bond. [ka] (In the formula, Rf is a monovalent perfluoropolyether group; A is a divalent organic group having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and silicon atoms; R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; x is an integer from 1 to 3; B is independently a monovalent organic group which has one or more diorganohydrosilyl groups and forms a silalkylene structure with the silicon atom to which it is linked; when x is 1, B has two or more diorganohydrosilyl groups; and y is 1 or 2.)

[0034] In the general formula (1), Rf is a monovalent perfluoropolyether group. Rf is introduced to impart compatibility with the base oil in a fluoropolyether-based curable composition (especially a thermosetting fluoropolyether-based composition). Compared with a perfluoroalkyl group, the perfluoropolyether group has a greater effect of imparting compatibility with the base oil when introduced into an organohydrogensilane compound, and can provide a fluoropolyether-based cured product with good properties.

[0035] In particular, Rf in the above general formula (1) is preferably a monovalent perfluoropolyether group represented by the following general formula (5). [ka] (In the formula, D represents a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms; a, b, c, and d each independently represent an integer of 0 to 100, and 2≦a+b+c+d≦100; preferably, a represents an integer of 0 to 50, b represents an integer of 0 to 50, c represents an integer of 0 to 50, and d represents an integer of 0 to 50, and 5≦a+b+c+d≦50; more preferably, a represents an integer of 0 to 10, b represents an integer of 0 to 40, c represents an integer of 0 to 30, and d represents an integer of 0 to 30, and 6≦a+b+c+d≦40; still more preferably, 7≦a+b+c+d≦30; and e represents an integer of 1 to 3. The repeating units shown in the parentheses may be bonded randomly, and these units may be linear or branched.)

[0036] In the above general formula (5), D is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms. The perfluorooxyalkyl group having 1 to 6 carbon atoms includes C g F 2g+1 O- (g is an integer of 1 to 6), and specific examples include groups represented by the following formulas. CF3O- CF3CF2O- CF3CF2CF2O- CF3CF(CF3)O- CF3CF2CF2CF2O- CF3CF2CF2CF2CF2CF2O- D is preferably a fluorine atom.

[0037] In the above general formula (5), if a+b+c+d is less than 2, the compatibility of the fluorine-containing organohydrogensilane compound with the base oil may decrease, which is undesirable. On the other hand, if a+b+c+d is greater than 100, the viscosity of the fluorine-containing organohydrogensilane compound increases, and the viscosity of the thermosetting fluoropolyether composition containing the fluorine-containing organohydrogensilane compound also increases too much, which is undesirable.

[0038] Examples of the monovalent perfluoropolyether group represented by the above general formula (5) include the following. [ka] (In the formula, g is an integer of 1 to 6, c' is an integer of 2 to 100, b' is an integer of 2 to 100, and e' is 2 or 3. c'' and d' are each an integer of 0 to 100, c''+d' is an integer of 2 to 100, and a' is an integer of 2 to 100. Each repeating unit shown in parentheses followed by c'' and d' may be bonded randomly.)

[0039] In the above general formula (1), A is a divalent organic group having 1 to 20 carbon atoms which may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and is preferably an alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 12 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 8 to 20 carbon atoms), or an alkylene group having 1 to 10 carbon atoms bonded to each other via a diorganosilylene group. Examples of suitable groups include a divalent group having an ether-bonded oxygen atom, a divalent group having an alkylene group of 1 to 10 carbon atoms and an arylene group of 6 to 8 carbon atoms bonded via a diorganosilylene group, and a divalent group having at least one bond selected from the group consisting of an ether-bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond. Of these, a divalent group containing at least one bond selected from the group consisting of an ether-bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond within the molecular chain is preferred. When A contains a silicon atom (diorganosilylene group), it is preferred that the silicon atom (diorganosilylene group) and the silicon atom to which A is bonded form a silalkylene structure in which the silicon atom (diorganosilylene group) is linked via an alkylene group (preferably an unsubstituted or fluorine-substituted alkylene group of 1 to 12 carbon atoms, more preferably an ethylene group).

[0040] Specifically, A is preferably represented by any one of the following general formulas (6) to (9). [ka] (In the formula, X 0 is a hydrogen atom, a methyl group, or an ethyl group, and X 1 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and X 2is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, R' is independently a methyl group or an ethyl group, f is an integer of 1 to 6, and t is 0 or 1. Note that the bond marked with * indicates that it is bonded to the Si atom in the above general formula (1), and the bond without a mark indicates that it is bonded to Rf.

[0041] Examples of the structure of A represented by the above general formulas (6) to (9) include the following. [ka] [ka] [ka] [ka] (In the formula, Me is a methyl group, and Et is an ethyl group. Note that the bond marked with * indicates that it is bonded to the Si atom in the above general formula (1), and the bond without a mark indicates that it is bonded to Rf.)

[0042] In the general formula (1), R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and specifically, is preferably a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, or a phenyl group, and more preferably a methyl group or an ethyl group.

[0043] In the general formula (1), B is a monovalent organic group having one or more diorganohydrosilyl groups and forming a silalkylene structure with the silicon atom to which it is linked, i.e., when x is 1, it has two or more, preferably 2 to 5, diorganohydrosilyl groups, and when x is 2 or 3, it independently has one or more, preferably 1 to 3, diorganohydrosilyl groups, and it is a monovalent silicon-containing organic group that forms a silalkylene structure with the silicon atom to which it is linked, and does not contain a siloxane bond. Note that the silalkylene structure is formed by connecting silicon atoms to each other through an unsubstituted and / or fluorine-substituted alkylene group R having 1 to 12 carbon atoms. APreferably, B has a structure in which B is linked via a silicon atom. Preferably, B has one or more silicon atoms, more preferably 1 to 6, and even more preferably 1 to 4. In formula (1), 1 to 3 B's are bonded to silicon atoms (x is an integer of 1 to 3), and preferably 2 or 3 B's are bonded (preferably, x is 2 or 3).

[0044] In addition, the continuous silalkylene structure in the molecular chain between Rf and the diorganohydrosilyl group in B in the general formula (1) (i.e., -A-Si-, -Si-(CH2) y Consecutive silalkylene bonds (-Si-R A The number of —Si—) is preferably 2 or more, and more preferably 2, 3 or 4.

[0045] B is preferably represented by the following general formula (10). [ka] [In the formula, p is an integer of 1 to 6, preferably an integer of 1 to 4; q is an integer of 0 to 6, preferably 0 or an integer of 4 to 6; r is an integer of 1 to 3; R is the same as above; E is a hydrogen atom or a group represented by the following formula: [ka] (wherein R is the same as above, p' is an integer of 1 to 6, preferably an integer of 1 to 4, and q' is an integer of 0 to 6, preferably an integer of 0 or 4 to 6) (provided that when E is a hydrogen atom, r is 1). The repeating units shown in parentheses with p, q or p', q' above may be bonded randomly.)

[0046] Like R in the general formula (1), R in the general formula (10) is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, and a phenyl group are particularly preferred.

[0047] Examples of B in the above general formula (1) include the following. [ka] [ka] [ka] (In the formula, Me is a methyl group, Et is an ethyl group, iPr is an isopropyl group, tBu is a tertiary butyl group, and Ph is a phenyl group.)

[0048] Examples of the fluorine-containing organohydrogensilane compound represented by the above general formula (1) include the following. [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, b' is an integer of 2 to 100, c''' and d'' are each an integer of 1 to 99, c'''+d''=an integer of 2 to 100, Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group. Each repeating unit shown in parentheses followed by c''' and d'' may be bonded randomly.)

[0049] [Method for producing fluorine-containing organohydrogensilane compounds] The method for producing the fluorine-containing organohydrogensilane compound represented by the above general formula (1), which is component (B), preferably comprises a step of introducing two or more diorganohydrosilyl groups with a predetermined linking structure into the fluorine-containing compound by a hydrosilylation reaction using, for example, an alkenyl group (vinyl group)-containing fluorine-containing compound represented by the following general formula (1A) and an organohydrogensilane compound having at least three diorganohydrosilyl groups represented by the following general formula (1B): [ka] [ka]

[0050] In general formula (1A), A 2 is a divalent organic group having 1 to 18 carbon atoms which may contain at least one atom selected from oxygen, nitrogen, and silicon atoms. The explanations for Rf, R, B, y, and x in the above general formulas (1A) and (1B) are the same as those for Rf, R, B, y, and x in the above general formula (1). That is, in the above general formulas (1A) and (1B), Rf is a monovalent perfluoropolyether group, R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, x is an integer of 1 to 3, B is independently a monovalent organic group which has one or more diorganohydrosilyl groups and forms a silalkylene structure with the silicon atom to which it is linked, and when x is 1, B has two or more diorganohydrosilyl groups. y is 1 or 2.

[0051] A 2is a divalent organic group (preferably a hydrocarbon group) having 1 to 18 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, and is an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 6 to 18 carbon atoms), a divalent group in which a diorganosilylene group is bonded to an alkylene group having 1 to 10 carbon atoms, a divalent group in which a diorganosilylene group is bonded to an arylene group having 6 to 8 carbon atoms, a divalent group in which an alkylene group having 1 to 10 carbon atoms and an alkylene group having 1 to 8 carbon atoms are bonded to a diorganosilylene group, Examples include divalent groups in which an alkylene group having 1 to 8 carbon atoms and an arylene group having 6 to 8 carbon atoms are bonded via a silylene group, divalent groups in which an alkylene group having 1 to 8 carbon atoms and an arylene group having 6 to 8 carbon atoms are bonded via a diorganosilylene group, and divalent groups in which these groups further contain at least one bond selected from an ether-bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond. Of these, divalent groups containing at least one bond selected from an ether-bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond within the molecular chain are preferred.

[0052] A 2 Specifically, the compound represented by any one of the following general formulas is preferred. [ka] [ka] (In the formula, X 0 , X 1 , X 2 , f are the same as above, and these explanations are based on X in the above formula (1). 0 , X 1 , X 2 The explanation for f is the same as above. f' is an integer of 0 to 4. The bond marked with an * indicates that the bond is bonded to the vinyl group in the above general formula (1A), and the bond without a mark indicates that the bond is bonded to Rf.

[0053] A represented by the above general formula 2 Examples of the structure include the following: [ka] [ka] [ka] [ka] (In the formula, Me is a methyl group, and Et is an ethyl group. The bond marked with an * indicates a bond to the vinyl group in the above general formula (1A), and the unmarked bond indicates a bond to Rf.)

[0054] The production steps (reaction formula) of a preferred method for producing a fluorine-containing organohydrogensilane compound are shown below. [ka]

[0055] The explanations for Rf, A, R, B, y, and x in the reaction scheme shown in the above steps are the same as those for Rf, A, R, B, y, and x in the general formula (1) above. 2 The explanation of A in the above general formula (1A) 2 The same as the explanation for M. M is a metal catalyst.

[0056] In the above step, a fluorine-containing compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the terminal of the molecular chain is subjected to a hydrosilylation reaction with an organohydrogensilane compound represented by the above general formula (1B) and having at least three diorganohydrosilyl groups in the molecule in the presence of a metal catalyst (M) to produce a fluorine-containing organohydrogensilane compound represented by the above general formula (1).

[0057] In the above reaction, the following compounds can be used, for example, as the fluorine-containing compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the molecular chain terminal. [ka] (In the formula, b' is an integer of 2 to 100, c''' and d'' are each an integer of 1 to 99, c'''+d''=an integer of 2 to 100, Me is a methyl group, and Et is an ethyl group. Each repeating unit shown in parentheses followed by c''' and d'' may be bonded randomly.)

[0058] As the organohydrogensilane compound represented by the above general formula (1B) and having at least three diorganohydrosilyl groups in the molecule, for example, the following compounds can be used. [ka] [ka] (In the formula, Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group.)

[0059] The amount of the fluorine-containing compound represented by the general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the molecular chain terminal is such that the amount of alkenyl groups in the fluorine-containing compound is 0.16 to 0.30 equivalents, preferably 0.20 to 0.25 equivalents, relative to the amount of hydrosilyl groups in the compound represented by the general formula (1B). If the amount of alkenyl groups in the fluorine-containing compound is less than 0.16 equivalents relative to the amount of hydrosilyl groups in the compound represented by the general formula (1B), the resulting fluorine-containing organohydrogensilane compound may cause cloudiness or viscosity increase when added to a fluoropolyether-based curable composition, or the cured product obtained by thermal curing may have uncured portions scattered on the surface, which is undesirable. Furthermore, if the amount of alkenyl groups in the fluorine-containing compound is more than 0.30 equivalents relative to the amount of hydrosilyl groups in the compound represented by the general formula (1A), the amount of hydrosilyl groups in the resulting fluorine-containing organohydrogensilane compound will be too small, making it difficult to cure the fluoropolyether-based curable composition, which is not preferred.

[0060] Furthermore, the hydrosilylation in the above reaction step can be accelerated by adding M (metal catalyst). M is not particularly limited as long as it is a metal catalyst capable of catalyzing hydrosilylation, but compounds containing metal atoms such as platinum, rhodium, ruthenium, and palladium are suitable. For example, chloroplatinic acid or a complex of chloroplatinic acid with an olefin such as ethylene, a complex of chloroplatinic acid with an alcohol or vinylsiloxane, metallic platinum supported on silica, alumina, carbon, or the like, RhCl(PPh3)3, RhCl(CO)(PPh3)2, Ru3(CO) 12 Examples include IrCl(CO)(PPh3)2, Pd(PPh3)4, etc. In the above formula, Ph is a phenyl group. Among them, platinum compounds are particularly preferred.

[0061] When using these catalysts, if they are solid catalysts, they can be used in solid form, but to promote the reaction more rapidly, it is preferable to use the metal catalyst dissolved in an appropriate solvent. The addition is preferably carried out after confirming that the system containing the fluorine-containing compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the molecular chain terminal and the organohydrogensilane compound represented by the above general formula (1B) and having at least three diorganohydrosilyl groups in the molecule is heated to a predetermined temperature. The predetermined temperature is preferably 50°C or higher, more preferably 65°C or higher.

[0062] When the fluorine-containing compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the molecular chain terminal or the organohydrogensilane compound represented by the above general formula (1B) and having at least three diorganohydrosilyl groups in the molecule is solid or when the compounds are insoluble with each other, they may be dissolved in a small amount of organic solvent and then M (metal catalyst) is added. Usable solvents include benzene, toluene, xylene, 1,3-bistrifluoromethylbenzene, etc., and 1,3-bistrifluoromethylbenzene is preferred.

[0063] The amount of hydrosilyl groups in the fluorine-containing organohydrogensilane compound of component (B) is preferably 0.05 to 0.35 mol / 100 g, and more preferably 0.06 to 0.30 mol / 100 g. 1 It can be measured by H-NMR (the same applies to the examples).

[0064] The amount of component (B) to be added is such that the amount of hydrogen atoms bonded to silicon atoms (hydrosilyl groups, i.e., Si-H groups) in component (B) is 0.1 to 2.5 moles, preferably 0.2 to 2 moles, per mole of alkenyl groups such as vinyl groups and allyl groups in component (A). If the amount of hydrosilyl groups is too small, the degree of crosslinking will be insufficient, making it impossible to obtain a cured product, while if the amount is too large, foaming will occur during curing.

[0065] In the method for producing the fluorine-containing organohydrogensilane compound of component (B), the target product may be isolated after completion of the reaction. Furthermore, as long as the properties of the present invention are not impaired, mixtures containing unreacted materials and by-products can also be used by removing the addition reaction catalyst. In either case, the amount of hydrosilyl groups, i.e., Si-H groups, should be 0.1 to 2.5 moles, preferably 0.2 to 2 moles, per mole of alkenyl groups, such as vinyl groups and allyl groups, in component (A).

[0066] As the component (B), these fluorine-containing organohydrogensilane compounds may be used alone or in combination of two or more.

[0067] [(C) component] Component (C) used in the fluoropolyether-based curable composition of the present invention is a platinum group metal catalyst. This is a hydrosilylation catalyst that promotes the addition reaction between the alkenyl groups in component (A) and the hydrosilyl groups in component (B) and the optional adhesion improver and adhesion promoter described below. Because these hydrosilylation catalysts are generally compounds of noble metals and are expensive, relatively readily available platinum or platinum compounds are often used.

[0068] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. As platinum group metal catalysts other than platinum compounds, rhodium, ruthenium, iridium, and palladium compounds are also known, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO). 12 Examples include IrCl(CO)(PPh3)2, Pd(PPh3)4, etc. In the above formula, Ph is a phenyl group.

[0069] When using these catalysts, if they are solid catalysts they can be used in solid form, but in order to obtain a more uniform cured product, it is preferable to use a solution of chloroplatinic acid or a complex in an appropriate solvent, which is then mixed with the perfluoropolyether compound of component (A).

[0070] The amount of component (C) used may be a catalytic amount, but for example, it is preferably 0.1 to 1,000 ppm (platinum group metal atom equivalent) relative to the mass of component (A), and more preferably 1 to 500 ppm. Component (C) can be used alone or in combination of two or more different compounds.

[0071] [Other ingredients] In order to enhance the practical utility of the fluoropolyether-based curable composition of the present invention, various additives may be added as needed, in addition to the above components (A) to (C), such as adhesion improvers (adhesion imparting agents), plasticizers, viscosity modifiers, flexibility imparting agents, hydrosilylation reaction catalyst inhibitors, inorganic fillers, adhesion promoters, silane coupling agents, etc. The amounts of these additives added are arbitrary as long as they do not impair the object of the present invention and do not impair the properties of the composition or the physical properties of the cured product.

[0072] The adhesion improver acts as an adhesion improver to impart self-adhesion to the fluoropolyether-based curable composition of the present invention when incorporated therein, and is an organohydrogenpolysiloxane compound having, per molecule, at least one silicon-bonded hydrogen atom (Si-H group) and at least one epoxy group and / or trialkoxysilyl group bonded to the silicon atom via a carbon atom or a carbon atom and an oxygen atom. Because the adhesion improver has a molecular structure corresponding to a fluorine-containing organohydrogensiloxane, it is difficult to maintain long-term self-adhesion to hydrofluoric acid or the electrolyte solution for lithium-ion secondary batteries by using the adhesion improver. However, it is extremely effective in cases where initial self-adhesion is required, such as during the manufacturing process of an article having a cured product obtained from the fluoropolyether-based curable composition of the present invention.

[0073] The above adhesion improver further preferably has one or more perfluoroalkyl groups or monovalent perfluoropolyether groups (perfluorooxyalkyl groups) bonded to silicon atoms via a divalent linking group containing at least one selected from oxygen atoms, nitrogen atoms, carbon atoms, and silicon atoms in one molecule, particularly a divalent linking group containing nitrogen atoms and carbon atoms, or a divalent linking group containing nitrogen atoms, carbon atoms, and oxygen atoms. Such perfluoroalkyl groups include C j F 2j+1 - (j is an integer of 1 to 10, preferably an integer of 3 to 7). Examples of the monovalent perfluoropolyether group include those exemplified as Rf in formula (1) shown in the component (B) above. As the divalent linking group connecting the perfluoroalkyl group or monovalent perfluoropolyether group to the silicon atom, a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and silicon atoms can be used.

[0074] The siloxane skeleton of the organohydrogenpolysiloxane compound of the adhesion improver may be cyclic, linear, branched, or a mixture of two or more of these, but is preferably cyclic. The organohydrogenpolysiloxane compound of the adhesion improver can be one represented by the following general formula:

[0075] [ka] (In the formula, R 2 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and L 1 is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group, and M 1 is an epoxy group or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, as shown below. w2 is preferably an integer satisfying 0≦w2≦50, more preferably an integer satisfying 0≦w2≦20, x2 is preferably an integer satisfying 1≦x2≦50, more preferably an integer satisfying 1≦x2≦20, y2 is preferably an integer satisfying 0≦y2≦50, more preferably an integer satisfying 1≦y2≦20, and z2 is preferably an integer satisfying 1≦z2≦50, more preferably an integer satisfying 1≦z2≦20. The repeating units shown in the above parentheses may be bonded randomly.

[0076] Above R 2 The unsubstituted or halogen-substituted monovalent hydrocarbon group is preferably one containing no aliphatic unsaturated bonds and having 1 to 10 carbon atoms, more preferably one containing 1 to 8 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenylethyl; and substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, and of these, a methyl group is particularly preferred.

[0077] The above L 1is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group, and is preferably represented by the following general formula: -Z-Rf 2 [In the formula, Rf 2 is a monovalent perfluoropolyether group, is the same as Rf in the above general formula (1), and can be exemplified by the same groups as those exemplified for Rf. Z is a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and silicon atoms.

[0078] Examples of Z include -CH2-*, -CH2CH2CH2-*, -OCH2-*, -CH2OCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -CH2-NH-CO-*, -(CH2)3-NH-CO-*, -(CH2)3-N( Me)-CO-*, -(CH2)3-N(Et)-CO-*, -(CH2)3-N(CH(Me)2)-CO-*, -CH2-N(Ph)-CO-*, -(CH2)3-O-CO-*, -CH2OCH2CH2CH2-Si(Me)2-O-Si(Me)2- Examples include (CH2)2-*, -CO-N(Me)-Ph'-Si(Me)2-(CH2)2-*, -CO-N(CH2)-Ph'-Si(CH2)2-(CH2)2-Si(CH2)2-O-Si(CH2)2-(CH2)2-*, -CO-NH-Ph'-[Si(Me)2-(CH2)2]3-CH2-*, -CO-N(Me)-Ph'-[Si(Me)2-(CH2)2]3-*, and groups represented by the following formulas, of which -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, and groups represented by the following formulas are preferred. Here, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Ph' represents a phenylene group. Furthermore, a bond marked with an * indicates that the bond is with a monovalent perfluoropolyether group, and a bond without an * indicates that the bond is with a silicon atom in the organohydrogenpolysiloxane. [ka]

[0079] The above M1 represents an epoxy group or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and specific examples include the following groups:

[0080] [ka] (In the formula, R 3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, optionally containing an oxygen atom (such as an alkylene group such as a methylene group, an ethylene group, or a propylene group, a cycloalkylene group such as a cyclohexylene group, or an oxyalkylene group such as an oxyethylene group, an oxypropylene group, or an oxybutylene group, preferably -(CH2)3OCH2-*' (the bond with *' indicates a bond to an epoxy group)).

[0081] -R 4 -Si(OR 5 )3 (In the formula, R 4 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, especially 1 to 4 carbon atoms (e.g., an alkylene group such as a methylene group, an ethylene group, or a propylene group), and R 5 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms (e.g., an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group).

[0082] [ka] (In the formula, R 6 is a hydrogen atom or a methyl group, and R 7 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms (e.g., an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group), and 1 represents an integer of 2 to 10.

[0083] The organohydrogenpolysiloxane compound used as an adhesion improver can be obtained by subjecting an organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms (Si-H groups) per molecule to a partial addition reaction, according to a conventional method, with a compound containing an aliphatic unsaturated group such as a vinyl group or an allyl group, an epoxy group and / or a trialkoxysilyl group, and optionally a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or a perfluorooxyalkyl group. Note that the number of the aliphatic unsaturated groups must be less than the number of Si-H groups.

[0084] In producing the organohydrogenpolysiloxane compound used as an adhesion promoter, the target substance may be isolated after the reaction is completed, but it is also possible to use the mixture from which only the unreacted materials and the addition reaction catalyst have been removed.

[0085] Specific examples of organohydrogenpolysiloxane compounds used as adhesion improvers include those represented by the following structural formulas. These compounds may be used alone or in combination of two or more. In the following formulas, Me represents a methyl group.

[0086] [ka] (wherein x2'=2 or 3, and b1'=an integer of 2 to 20. The repeating units shown in parentheses may be bonded randomly.)

[0087] [ka] (wherein x2'=2 or 3, and b1'=an integer of 2 to 20. The repeating units shown in parentheses may be bonded randomly.)

[0088] [ka] (wherein x2''=1 or 2, and b1'=an integer of 2 to 20. The repeating units shown in parentheses may be bonded randomly.)

[0089] [ka] (wherein z2' is 2 or 3, and b1' is an integer of 2 to 20. The repeating units shown in parentheses may be bonded randomly.)

[0090] [ka] (wherein y2'=2 or 3, and b1'=an integer of 2 to 20. The repeating units shown in parentheses may be bonded randomly.)

[0091] When an adhesion improver is added, the amount added is preferably an amount such that the number of hydrosilyl groups (Si-H groups) in the adhesion improver per mole of alkenyl groups in component (A) is 0.005 to 0.5 moles, more preferably 0.01 to 0.2 moles, and even more preferably 0.05 to 0.1 moles.

[0092] As the plasticizer, viscosity modifier, and flexibility imparting agent, a polyfluoromonoalkenyl compound represented by the following general formula (12) and / or a polyfluoro compound represented by the following general formulas (13) and (14) can be used.

[0093] Rf 3 -(Z 1 ) p2 CH=CH2(12) [In the formula, Z 1 is a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, p2 is 0 or 1, and Rf 3 is a monovalent perfluoropolyether group represented by the following general formula: [ka] (wherein f2 is an integer of 2 to 200, preferably an integer of 2 to 100, h2 is an integer of 1 to 3, and Rf in formula (2) in the component (A) used 1 (molecular weight less than that of

[0094] Y 1 -O-(CF2CF2CF2O) c2 -Y 1 (13) [In the formula, Y 1 are independently of each other by the formula: C k2 F 2k2+1 - (k2 is an integer of 1 to 3), c2 is an integer of 1 to 200, and Rf in formula (2) in the component (A) used is 1 smaller than the molecular weight of

[0095] Y 2 -O-(CF2O) d2 (CF2CF2O) e2 -Y 2 (14) (In the formula, Y 2 is the above Y 1 where d2 and e2 are each an integer of 1 to 200, and Rf in formula (2) in the component (A) used is the same as 1 The molecular weight is smaller than that of the repeating units shown in the parentheses above.

[0096] In the above general formula (12), Z 1 is a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms and silicon atoms, and the above L 1 In addition to the same as Z (divalent linking group) in the structure, the following can be further exemplified (in the following and exemplary formulas of Z, the bond with * represents Rf 3 A bond without an * indicates a bond to a carbon atom. Also, Me indicates a methyl group.) [ka]

[0097] Specific examples of the polyfluoromonoalkenyl compound represented by the above general formula (12) include the following: The following f2 satisfies the above requirements.

[0098] [ka]

[0099] Specific examples of polyfluoro compounds represented by the above general formulas (13) and (14) include the following: Note that c2, d2, e2, and the sum of d2 and e2 below satisfy the above requirements. CF3O-(CF2CF2CF2O) c2 -CF2CF3 CF3-O-(OCF2) d2 (OCF2CF2) e2 -CF3

[0100] The viscosity (23° C.) of the polyfluoromonoalkenyl compound of the above formula (12) and the polyfluoro compounds of the above formulas (13) and (14) is preferably in the range of 2,000 to 50,000 mPa·s. Furthermore, when the polyfluoromonoalkenyl compound of the above formula (12) and the polyfluoro compounds of the above formulas (13) and (14) are blended, the blending amount is preferably 1 to 300 parts by mass, more preferably 50 to 250 parts by mass, per 100 parts by mass of component (A).

[0101] Examples of inhibitors for hydrosilylation catalysts include acetylenic alcohols such as ethynylcyclohexanol (also known as 1-ethynyl-1-hydroxycyclohexane), 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol; reaction products of the above-mentioned monovalent fluorine-containing chlorosilanes with acetylenic alcohols; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and triallyl isocyanurate; polyvinylsiloxanes; and organic phosphorus compounds, the addition of which can maintain appropriate curing reactivity and storage stability. The amount of inhibitor used can be any amount within the range that can impart the desired curing properties and storage stability.

[0102] Examples of inorganic fillers that can be added include silica powders such as fumed silica (fumed silica or dry silica), precipitated silica (wet silica), spherical silica (fused silica), sol-gel silica, and silica aerogel; various surface-treated silica powders obtained by hydrophobizing the untreated surface of the silica powder with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, and the like; quartz powder, fused quartz powder, diatomaceous earth, and reinforcing or semi-reinforcing fillers such as calcium carbonate; inorganic pigments such as titanium oxide, iron oxide, carbon black, and cobalt aluminate; heat resistance improvers such as titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate; thermal conductivity imparting agents such as alumina, boron nitride, silicon carbide, and metal powder; and conductivity imparting agents such as carbon black, silver powder, and conductive zinc oxide.

[0103] When the fluoropolyether-based curable composition of the present invention contains the adhesion promoter, the adhesion promoter serves to improve the adhesion-imparting ability of the adhesion improver and promote the self-adhesion of the cured product obtained by curing the fluoropolyether-based curable composition of the present invention. In particular, carboxylic acid anhydrides can be preferably used.

[0104] Examples of carboxylic acid anhydrides include those that are solid at 23° C. Specific examples include the following compounds: In the following formula, Me represents a methyl group. [ka]

[0105] The carboxylic acid anhydride may also be a cyclic organopolysiloxane (i.e., a fluorine-containing organopolysiloxane-modified carboxylic acid anhydride compound) having, in one molecule, a hydrogen atom directly bonded to a silicon atom, a perfluoroalkyl or perfluorooxyalkyl group bonded to the silicon atom via a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and silicon atoms, and a cyclic carboxylic acid anhydride residue bonded to the silicon atom via a divalent hydrocarbon group. An example of such a compound is one represented by the following general formula (15): Since this fluorine-containing organopolysiloxane-modified carboxylic acid anhydride compound has a molecular structure corresponding to that of a fluorine-containing organohydrogensiloxane, it is difficult to maintain long-term self-adhesion to hydrofluoric acid, electrolytes for lithium-ion secondary batteries, etc., by using this compound. However, it is extremely effective in cases where initial self-adhesion is required, such as during the manufacturing process of an article having a cured product obtained from the fluoropolyether-based curable composition of the present invention. [ka] (In the formula, L 2 are independently a monovalent perfluoropolyether group bonded to a silicon atom via a divalent hydrocarbon group, J is independently a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group, and R 8 are independently unsubstituted or halogen-substituted monovalent hydrocarbon groups, t2 is an integer of 1 to 6, u2 is an integer of 1 to 4, v2 is an integer of 1 to 4, and t2+u2+v2 is an integer of 4 to 10. The repeating units shown in the above parentheses may be bonded randomly.

[0106] In the above formula (15), L2 is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent hydrocarbon group, and the above L 1 These are groups that are introduced from the viewpoints of compatibility with component (A), dispersibility, uniformity after curing, and the like.

[0107] In addition, in the above formula (15), R 8 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and R 2 The same groups as those listed above can be mentioned, and a methyl group and an ethyl group are preferred.

[0108] In the above formula (15), J is a cyclic carboxylic acid anhydride residue bonded to a silicon atom via a divalent hydrocarbon group, and specific examples include groups represented by the following general formula: [ka]

[0109] In the above formula, R 9 is a divalent hydrocarbon group having 2 to 15 carbon atoms, and specific examples thereof include an ethylene group, a propylene group, and a butylene group, with a propylene group being preferred.

[0110] Furthermore, in the above formula (15), t2 is an integer of 1 to 6, preferably an integer of 2 to 5, u2 is an integer of 1 to 4, preferably an integer of 1 to 3, v2 is an integer of 1 to 4, preferably an integer of 1 to 3, and t2+u2+v2 is an integer of 4 to 10, preferably an integer of 4 to 8. However, ((H)(R 8 )SiO) units, ((L 2 )(R 8 )SiO) units, and ((J)(R 8 The arrangement order of the SiO) units is random.

[0111] Examples of the cyclic organopolysiloxane represented by the general formula (15) include the following compounds: In the following formula, Me represents a methyl group. [ka] (In the formula, t2'=2 or 3, and b2'=an integer of 2 to 20.) [ka] (In the formula, v2'=2 or 3, and b2'=an integer of 2 to 20.)

[0112] These adhesion promoters may be used alone or in combination of two or more, and in this case, the above-mentioned carboxylic acid anhydride that is solid at 23°C may be used in combination with the above-mentioned cyclic organopolysiloxane (fluorine-containing organopolysiloxane-modified carboxylic acid anhydride compound).

[0113] When an adhesion promoter is added, the amount added is preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of component (A).Furthermore, it is preferable that the amount of hydrosilyl groups (Si-H groups) in the adhesion promoter be 0.005 to 0.5 mol, and particularly 0.05 to 0.1 mol, per 1 mol of alkenyl groups in component (A). It is preferable that the total amount of hydrosilyl groups contained in the composition (particularly the total amount of hydrosilyl groups in component (B), the adhesion improver, and the adhesion promoter) is 0.1 to 2.5 moles, and particularly 0.2 to 2 moles, per mole of alkenyl groups in component (A).

[0114] [Method for producing fluoropolyether-based curable composition] The method for producing the fluoropolyether-based curable composition of the present invention is not particularly limited, and it can be produced by kneading the above-mentioned components. Specifically, the fluoropolyether-based curable composition of the present invention can be produced by uniformly mixing the above-mentioned components (A) to (C) and other optional components using a mixing device such as a planetary mixer, a Ross mixer, or a Hobart mixer, and if necessary, a kneading device such as a kneader or a three-roll mill. Alternatively, the composition may be made into a two-part composition, which are mixed at the time of use.

[0115] The produced fluoropolyether-based curable composition can be cured at room temperature depending on the type of catalyst used as component (C), but it is preferable to heat it to accelerate curing. In particular, to achieve good adhesion to various substrates, it is preferable to cure it at 60°C or higher, preferably 100 to 200°C, for a period of several minutes to several hours.

[0116] When using the fluoropolyether-based curable composition of the present invention, the composition may be dissolved to a desired concentration in an appropriate fluorine-based solvent, such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M Co.), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, etc., depending on the application and purpose. In particular, the use of a solvent is preferred for thin film coating applications.

[0117] The fluoropolyether-based curable composition of the present invention is preferably used as an electric or electronic part for automobiles, chemical plants, semiconductor production lines, analytical or physical / chemical instruments, living environments, communication devices, communication facilities, aircraft, railway vehicles, portable devices, power storage devices, robots, or lithium ion batteries. Particularly preferred are electric and electronic parts in which the cured product of the fluoropolyether-based curable composition of the present invention is used as a gasket, packing, protective seal or coating layer. [Example]

[0118] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, Me in the formulas represents a methyl group, and parts represent parts by mass. The number average molecular weight was determined as the number average molecular weight converted into polystyrene by gel permeation chromatography (GPC) analysis using AK-225 (manufactured by Asahi Glass Co., Ltd.), a fluorine-based solvent, as the developing solvent. The viscosity (23°C) indicates a value measured in accordance with the method of viscosity testing using a rotational viscometer specified in JIS K6249.

[0119] Synthesis of fluorine-containing organohydrogensilane compounds [Synthesis Example 1] In a 1 L flask, an organohydrogensilane compound (hydrosilyl group amount 0.616 mol / 100 g) represented by the following formula (16) was added. [ka] 150g and a compound represented by the following formula (17) (vinyl group amount 0.0681mol / 100g) [ka] 339g of a distillate and 91g of 1,3-bistrifluoromethylbenzene were charged, and the atmosphere was purged with nitrogen. After heating to 70°C, 0.16 g of (C1) a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass) was added dropwise and stirred at 85°C for 1 hour. The reaction solution was quenched and concentrated under reduced pressure. The resulting residue was dissolved in FC-3283 (524 g) and stirred with 9.10 g of activated carbon (Shirasagi AS, manufactured by Osaka Gas Chemicals) for 1 hour, followed by filtration. Activated carbon (9.10 g) was added to the resulting solution, stirred for 1 hour, and then filtered. The main component was extracted from the obtained solution by preparative liquid chromatography, and then concentrated under reduced pressure to obtain a compound represented by the following formula (18) (hydrosilyl group amount: 0.143 mol / 100 g): [ka] 376g of the obtained product 1 The H-NMR spectrum confirmed the following signals: δ 7.86-6.55 (m, 4H), 4.38-3.64 (m, 3H), 3.15 (s, 3H), 2.46-1.48 (br, 4H), 1.18--0.91 (m, 52H), confirming the production of the compound represented by formula (18).

[0120] [Synthesis Example 2] Instead of the compound represented by the formula (17), a compound represented by the following formula (19) (vinyl group amount: 0.0228 mol / 100 g) [ka] The same procedure as in Synthesis Example 1 was repeated except that 1,012 g of the compound represented by the following formula (20) (amount of hydrosilyl group: 0.0682 mol / 100 g) was used. [ka] 741 g of the obtained product 1 The H-NMR spectrum confirmed the following signals: δ 7.68-6.36 (m, 4H), 4.21-3.44 (s, 3H), 3.03 (s, 3H), 2.29-1.41 (br, 4H), 1.13--0.98 (m, 52H), confirming the production of the compound represented by formula (20) above.

[0121] [Synthesis Example 3] Instead of the compound represented by the formula (16), a compound represented by the following formula (21) (hydrosilyl group amount: 1.09 mol / 100 g) [ka] The same procedure as in Synthesis Example 1 was repeated except that 85 g of the compound represented by the following formula (22) (amount of hydrosilyl group: 0.247 mol / 100 g) was used. [ka] 323 g of the obtained product 1 The H-NMR spectrum confirmed the following signals: δ 7.85 to 6.55 (m, 4H), 4.29 to 3.51 (m, 5H), 3.15 (s, 3H), and 1.23 to −0.91 (m, 62H), confirming the production of the compound represented by formula (22).

[0122] [Synthesis Example 4] Instead of the compound represented by the formula (17), a compound represented by the following formula (23) (vinyl group amount: 0.0873 mol / 100 g) [ka] (mean of m+n = 12, m:n = 0.98:1) The same procedure as in Synthesis Example 1 was repeated except that 264 g of the compound represented by the following formula (24) (amount of hydrosilyl group: 0.169 mol / 100 g) was used. [ka] (mean of m+n = 12, m:n = 0.98:1) 317g of the obtained product 1 The H-NMR spectrum confirmed the following signals: δ 6.89-6.61 (s, 1H), 4.39-3.66 (m, 3H), 3.41-3.07 (m, 2H), 2.46-1.47 (br, 4H), 1.74-1.39 (m, 2H), and 1.18--0.90 (m, 4H), confirming the production of the compound represented by formula (24).

[0123] <Preparation of fluoropolyether-based curable composition, confirmation of compatibility between component (B) and component (A) (base oil)> [Example 1] A curable composition was prepared by mixing 100 parts of (A1) polymer represented by formula (25) below (number average molecular weight 15,550, viscosity 10,900 mPa s, vinyl group content 0.012 mol / 100 g), with 0.1 parts of (C1) platinum-divinyltetramethyldisiloxane complex toluene solution (platinum concentration 0.5% by mass), 0.07 parts of compound represented by formula (26) below, and 9.74 parts of (B1) compound represented by formula (18) below obtained in Synthesis Example 1 (hydrosilyl group content 0.143 mol / 100 g). This demonstrated high compatibility between components (B1) and (A1). The composition was obtained as a clear oil. [ka] (In the formula, m and n are integers of 1 or more, and the average value of m+n is 90.) [ka] [ka]

[0124] [Example 2] A curable composition was prepared in the same manner as in Example 1, except that 100 parts of (A2) polymer represented by the following formula (27) (number average molecular weight 15,630, viscosity 11,000 mPa s, vinyl group content 0.012 mol / 100 g) was used instead of (A1) polymer represented by the above formula (25). The composition was obtained as a transparent oil. This demonstrated that the components (B1) and (A2) are highly compatible with each other. [ka] (In the formula, m and n are integers of 1 or more, and the average value of m+n is 90.)

[0125] [Example 3] A curable composition was prepared in the same manner as in Example 1, except that 100 parts of (A3) the polymer represented by the following formula (28) (number average molecular weight 3,350, viscosity 60 mPa s, vinyl group content 0.031 mol / 100 g) and 25.16 parts of (B1) the compound represented by the above formula (18) were used instead of (A1) the polymer represented by the above formula (25). The composition was obtained as a transparent oil. This demonstrated that the components (B1) and (A3) are highly compatible. [ka] (m:n=0.98:1, mean of m+n=34)

[0126] [Example 4] In Example 1, a curable composition was prepared in the same manner as in Example 1, except that 20.42 parts of (B2) the compound represented by the following formula (20) (hydrosilyl group amount: 0.0682 mol / 100 g) obtained in Synthesis Example 2 was used instead of (B1) the compound represented by the above formula (18). The composition was obtained as a transparent oil. This demonstrated that the compatibility between component (B2) and component (A1) was high. [ka]

[0127] [Example 5] In Example 1, a curable composition was prepared in the same manner as in Example 1, except that 5.73 parts of (B3) the compound represented by the following formula (22) (hydrosilyl group amount: 0.247 mol / 100 g) obtained in Synthesis Example 3 was used instead of (B1) the compound represented by the above formula (18). The composition was obtained as a transparent oil. This demonstrated that the components (B3) and (A1) are highly compatible with each other. [ka]

[0128] [Example 6] In Example 1, a curable composition was prepared in the same manner as in Example 1, except that 8.24 parts of (B4) the compound represented by the following formula (24) (hydrosilyl group amount: 0.169 mol / 100 g) obtained in Synthesis Example 4 was used instead of (B1) the compound represented by the above formula (18). The composition was obtained as a transparent oil. This demonstrated that the components (B4) and (A1) are highly compatible with each other. [ka] (m:n=0.98:1, mean of m+n=12)

[0129] [Example 7] In Example 1, instead of (B1) the compound represented by formula (18) above, 9.61 parts of (B5) a mixture of the compound represented by formula (18) above and the compounds represented by formulas (29), (30), (31), and (32) below (mass ratio: (18) / (29) / (30) / (31) / (32) = 80:9:6:1:4, hydrosilyl group content: 0.145 mol / 100 g) was used, which was obtained in the same manner as in Synthesis Example 1, except that the solution obtained in Synthesis Example 1 was directly concentrated under reduced pressure without extracting the main component by preparative liquid chromatography. A curable composition was prepared in the same manner as in Example 1, and obtained as a transparent oil. This demonstrated that component (B5) and component (A1) are highly compatible. [ka] [ka] [ka] [ka]

[0130] [Comparative Example 1] A curable composition was prepared in the same manner as in Example 1, except that 2.26 parts of (B6) the compound represented by the above formula (32) (hydrosilyl group amount: 0.616 mol / 100 g) was used instead of (B1) the compound represented by the above formula (18). The composition was obtained as a cloudy oil. This indicated that the compatibility between the (B6) component and the (A1) component was low.

[0131] Comparative Example 2 In Example 1, a curable composition was prepared in the same manner as in Example 1, except that 3.52 parts of (B7) compound represented by the following formula (33) (Patent Document 5: the compound described in Example 1 of JP-A No. 2002-012769, hydrosilyl group amount: 0.408 mol / 100 g) was used instead of (B1) compound represented by the above formula (18). The composition was obtained as a slightly cloudy white oil. This indicated that the compatibility between component (B7) and component (A1) was low. [ka]

[0132] Comparative Example 3 A curable composition was prepared in the same manner as in Example 1, except that 3.54 parts of (B8), a compound represented by the following formula (34) (hydrosilyl group amount: 0.394 mol / 100 g), was used instead of (B1), a compound represented by the above formula (18). The composition was obtained as a transparent oil. This demonstrated that the compatibility between the (B8) component and the (A1) component was high. [ka]

[0133] <Confirming the presence of oily components (uncured areas) on the surface of fluoropolyether-based cured products, and evaluating the release properties of the cured products> The fluoropolyether-based curable compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were poured into a 2 mm thick stainless steel mold placed on a Teflon (registered trademark, the same applies hereinafter) sheet, sandwiched between other Teflon sheets, and press-cured at 150°C for 10 minutes. After press-curing, the 2 mm thick stainless steel mold was removed, and the resulting fluoropolyether-based cured products were evaluated for releasability and residual oily components on the surface of the cured products according to the following criteria. The results, along with the appearance of the fluoropolyether-based curable compositions, are shown in Table 1. [Evaluation criteria] ◯: The cured product could be easily peeled off from the Teflon sheet without being damaged, and no oily components were found remaining on the surface of the peeled cured product. ×: It was difficult to peel the cured product from the Teflon sheet without damaging it, and residual oily components were found on the surface of the peeled cured product.

[0134] [Table 1]

[0135] In the fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Example 3, no scattered uncured oily components were observed on the surface of the cured products. This is because the component (B) contained in the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Example 3 exhibited high compatibility with the component (A), resulting in the reaction of almost all of the component (B) with the component (A). Furthermore, the cured products could be easily peeled off from the Teflon sheet after press curing, confirming that there were no problems with releasability. On the other hand, scattered uncured oily components were observed on the surface of the fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Comparative Examples 1 and 2. This is thought to be due to the poor compatibility of the components (B6) and (B7) with the component (A), which resulted in insufficient reaction with the component (A) during thermal curing, resulting in the unreacted material remaining as an oily component on the surface of the fluoropolyether-based cured product. Furthermore, the press cure caused the cured product to adhere to the Teflon sheet, resulting in poor releasability, such as the cured product breaking or being damaged when peeled off the Teflon sheet.

[0136] The fluoropolyether-based cured product obtained above was post-cured at 200°C for 4 hours, and then evaluated for heat resistance, chemical resistance, solvent resistance, and electrolyte resistance. The results are shown in Tables 2 to 5.

[0137] <Heat resistance> The physical properties of the fluoropolyether cured products obtained from the fluoropolyether curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated in accordance with JIS K 6249. Next, the fluoropolyether cured products obtained from the fluoropolyether curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were left in an oven at 150°C for 7 days, and the physical properties of the cured products were evaluated in accordance with JIS K 6249. The change in hardness, change in tensile strength (%), and change in elongation at break (%) were calculated using the following formulas. The results are shown in Table 2.

[0138] Hardness change = (hardness of cured product after 7 days at 150°C) - (initial hardness of cured product) Tensile strength change rate (%) = ((tensile strength of cured product after 7 days at 150°C) - (initial tensile strength of cured product)) / (initial tensile strength of cured product) × 100 Change in elongation at break (%) = ((elongation at break of cured product after 7 days at 150°C) - (initial elongation at break of cured product)) / (initial elongation at break of cured product) × 100

[0139] [Table 2]

[0140] <Chemical resistance> The fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were immersed in concentrated hydrochloric acid, concentrated sulfuric acid, concentrated hydrofluoric acid, trifluoroacetic acid, or a 40% by mass aqueous solution of potassium hydroxide (KOH) at 20°C for 3 days, and the change in hardness was measured based on the hardness before immersion. The change in hardness was calculated using the same formula as in the heat resistance test. The results are shown in Table 3.

[0141] [Table 3]

[0142] The results in Table 3 confirm that the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 and 2 have excellent durability against all of the above chemicals. On the other hand, it was confirmed that the cured product obtained from the fluoropolyether-based curable composition of Comparative Example 3 has poor durability against concentrated hydrofluoric acid and trifluoroacetic acid.

[0143] <Solvent resistance> The fluoropolyether-based cured products (cured product samples) obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were subjected to immersion tests (immersion time: 70 hours) in various organic solvents shown in Table 4 in accordance with JIS K 6258. The volume change (%) before and after immersion was measured to evaluate the solvent swelling resistance. The results are shown in Table 4.

[0144] [Table 4] *1) IPA: Isopropyl alcohol *2) MEK: Methyl ethyl ketone *3)THF: Tetrahydrofuran

[0145] From the results in Table 4, it was confirmed that the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 had excellent durability against all of the above-mentioned solvents, similar to the cured products obtained from the curable fluoropolyether-based curable compositions of Comparative Examples 1 to 3.

[0146] <Electrolyte resistance> The fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were immersed in a lithium-ion battery electrolyte (manufactured by Kishida Chemical Co., Ltd.) at 80°C for 3 days, and the degree of deterioration of the cured products was evaluated according to the following evaluation criteria based on the changes in hardness, stickiness, and appearance of the cured products before and after immersion.

[0147] [Evaluation criteria] [Hardness] ◯: Almost no change in hardness was observed before and after immersion in the lithium ion battery electrolyte. ×: A significant decrease in hardness was observed due to immersion in the electrolyte for lithium ion batteries. [Sticky] ◯: There was no change in stickiness of the cured product surface due to immersion in the lithium ion battery electrolyte. ×: The surface of the cured product became sticky after immersion in the electrolyte for lithium ion batteries. 〔exterior〕 ◯: Almost no change in appearance was observed before and after immersion in the lithium ion battery electrolyte. ×: Swelling, deformation, and decomposition of the cured product were observed upon immersion in the electrolyte for lithium ion batteries.

[0148] [Table 5]

[0149] The cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 and 2 showed almost no change in hardness, surface stickiness, or appearance before and after immersion in the electrolyte solution for lithium ion batteries. This demonstrated that the above compositions and cured products are applicable to lithium ion batteries. On the other hand, the cured product obtained from the fluoropolyether-based curable composition of Comparative Example 3 showed changes such as swelling and surface decomposition upon immersion in the electrolyte solution for lithium ion batteries. Furthermore, the cured product easily tore when pulled at both ends.

[0150] From the above results, it was found that the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 had both durability against hydrofluoric acid and lithium ion battery electrolyte and releasability, demonstrating the effects of the present invention.

Claims

1. (A) a perfluoropolyether compound having two or more alkenyl groups in one molecule; (B) a fluorine-containing organohydrogensilane compound represented by the following general formula (1), which does not contain a siloxane bond in the molecule and has two or more hydrosilyl groups, and 【Chemistry 1】 (In the formula, Rf is a monovalent perfluoropolyether group; A is a divalent organic group having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and silicon atoms; R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; x is an integer from 1 to 3; B is independently a monovalent organic group which has one or more diorganohydrosilyl groups and forms a silalkylene structure with the silicon atom to which it is linked; when x is 1, B has two or more diorganohydrosilyl groups; and y is 1 or 2.) (C) Platinum group metal catalyst A lithium ion battery comprising a cured product of a fluoropolyether-based curable composition comprising:

2. 2. The lithium ion battery according to claim 1, wherein the base oil in the fluoropolyether-based curable composition comprises component (A).

3. 2. The lithium ion battery according to claim 1, wherein the fluoropolyether-based curable composition does not contain a reinforcing filler.

4. 2. The lithium ion battery according to claim 1, wherein the fluoropolyether-based curable composition does not contain an organohydrogenpolysiloxane compound having, in one molecule, at least one hydrogen atom bonded to a silicon atom and at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom.

5. 2. The lithium ion battery according to claim 1, wherein the component (A) in the fluoropolyether-based curable composition is a perfluoropolyether compound represented by the following general formula (2): 【Chemistry 2】 [In the formula, A 1 are independently divalent organic groups having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and silicon atoms; B 1 is a carbon atom or a silicon atom, and X is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least two of X are alkenyl groups having 2 to 8 carbon atoms, and when X is a hydrogen atom, the B to which it is bonded 1 is a carbon atom. 1 is a divalent perfluoropolyether group.

6. 2. The lithium ion battery according to claim 1, wherein in the component (B) of the fluoropolyether-based curable composition, Rf in the general formula (1) is a group represented by the following general formula (5): 【Transformation 3】 (In the formula, D is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms; a, b, c, and d each independently represent an integer of 0 to 100, with 2≦a+b+c+d≦100; and e is an integer of 1 to 3. The repeating units shown in the parentheses may be bonded randomly, and these units may be linear or branched.)

7. In the component (B) in the fluoropolyether-based curable composition, A in the general formula (1) is selected from alkylene groups having 1 to 12 carbon atoms, alkylene groups containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups are bonded to each other via a diorganosilylene group, divalent groups in which an alkylene group and an arylene group are bonded to each other via a diorganosilylene group, and divalent groups in which an ether-bonded oxygen atom, a secondary amino group, a tertiary amino group, and an amide bond are further bonded to these groups. The lithium ion battery according to claim 1,

8. In the component (B) in the fluoropolyether-based curable composition, A in the general formula (1) is any one of groups represented by the following general formulas (6) to (9). The lithium ion battery according to claim 1. 【Chemistry 4】 (In the formula, X 0 is a hydrogen atom, a methyl group, or an ethyl group, and X 1 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and X 2 is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, R' is independently a methyl group or an ethyl group, f is an integer of 1 to 6, and t is 0 or 1. Note that the bond marked with an * indicates that it is bonded to the Si atom in the above general formula (1), and the bond without a mark indicates that it is bonded to Rf.

9. 2. The lithium ion battery according to claim 1, wherein in the component (B) in the fluoropolyether-based curable composition, R in the general formula (1) is any one of a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, and a phenyl group.

10. 2. The lithium ion battery according to claim 1, wherein in the component (B) in the fluoropolyether-based curable composition, there are two or more consecutive silalkylene structures in the molecular chain between Rf in the general formula (1) and the diorganohydrosilyl group in B.

11. 2. The lithium ion battery according to claim 1, wherein in the component (B) in the fluoropolyether-based curable composition, B in the general formula (1) is a group represented by the following general formula (10): 【Transformation 5】 [In the formula, p is an integer of 1 to 6, q is an integer of 0 to 6, r is an integer of 1 to 3, R is the same as above, and E is a hydrogen atom or a group represented by the following formula: 【Transformation 6】 (wherein R is the same as above, p' is an integer of 1 to 6, and q' is an integer of 0 to 6) (provided that when E is a hydrogen atom, r is 1). The repeating units shown in parentheses with p, q or p', q' may be bonded randomly.]

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