Fluoropolyether-based curable compositions and cured products, and lithium-ion batteries

Abstract

Provided is a fluoropolyether-based curable composition comprising: (A) a perfluoropolyether compound having at least two alkenyl groups per molecule; (B) a fluorinated organohydrosilane compound represented by general formula (1) and having at least two hydrosilyl groups (in the formula, Rf represents a monovalent perfluoropolyether group; A represents a bivalent organic group; R represents a monovalent hydrocarbon group; x represents 1 to 3; B represents a monovalent organic group having a diorganohydrosilyl group and forms a silalkylene structure in conjunction with a silicon atom to which B is linked; and y represents 1 or 2); and (C) a platinum-group metal-based catalyst. The fluoropolyether-based curable composition can provide a cured article that has durability against hydrofluoric acid or an electrolyte solution for lithium ion batteries, does not undergo the formation of uncured portions due to the poor compatibility between the constituent components and has satisfactory mold-release properties.

Description

[Technical Field]

[0001] The present invention provides a fluoropolyether-based curable composition that has durability against hydrofluoric acid and electrolytes for lithium-ion batteries, and a cured product that has good release properties without uncured areas due to low compatibility between constituent components, and a cured product of the composition, and a cured product having the cured product. Lithium-ion battery Regarding. [Background technology]

[0002] Fluoropolyether-based curable compositions utilizing the addition reaction between alkenyl groups and hydrosilyl groups are known. For example, a composition has been proposed containing a fluoropolyether compound (hereinafter also referred to as "base oil") having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule, and a platinum group metal compound (Patent Document 1: JP-A-8-199070, Patent Document 2: JP-A-2011-201940). Furthermore, a composition has been proposed in which self-adhesive properties are imparted by adding an organopolysiloxane having a hydrosilyl group and an epoxy group and / or a trialkoxysilyl group to the composition as a third component (adhesion improver) (Patent Document 3: JP-A-9-95615, Patent Document 4: JP-A-2011-219692). This 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, and electrical properties, and is therefore used in various industrial fields where these properties are required.

[0003] Fluoropolyether-based curable compositions containing fluorine-containing organohydrogen siloxanes having two or more hydrogen atoms directly bonded to silicon atoms in one molecule contain siloxane bonds that are unstable to acids and could not exhibit sufficient performance in applications requiring high levels of acid resistance. In particular, they had low durability against hydrofluoric acid and were unsuitable for applications such as components for semiconductor manufacturing equipment. In response to this, it has been proposed to improve the acid resistance of fluoropolyether-based cured products by using a fluorine-containing organohydrogen silane compound that does not contain siloxane bonds and has two or more hydrogen atoms directly bonded to silicon atoms in one molecule, instead of the fluorine-containing organohydrogen siloxane (Patent Document 5: Japanese Patent Application Publication No. 2002-012769).

[0004] On the other hand, the above-mentioned fluorine-containing organohydrogen silane compounds tend to have a large proportion of the total molecule consisting of unfluorinated organic structures. This is largely due to the synthetic advantages of the fluorine-containing organohydrogen silane compounds. In this case, the short-chain perfluoroalkylene groups have poor compatibility with the base oil. Due to these tendencies, when a fluorine-containing organohydrogen silane compound is added to a fluoropolyether-based curable composition, the fluoropolyether-based curable composition sometimes becomes cloudy and its viscosity increases. Furthermore, oily uncured portions sometimes appear on the surface of the fluoropolyether-based cured product obtained from the fluoropolyether-based curable composition. The presence of these uncured portions often impairs the release properties of the fluoropolyether-based cured product, and this is undesirable because it can cause problems during the manufacturing process of articles containing the cured product, such as the cured product not peeling off from parts in the manufacturing equipment and hindering smooth manufacturing.

[0005] In recent years, due to growing concern about environmental issues, the development of products using lithium-ion batteries has been actively pursued worldwide. However, it has been found that fluoropolyether-based curable compositions and their cured products containing fluorine-containing organohydrogen siloxanes having two or more hydrogen atoms directly bonded to silicon atoms in one molecule have low durability against lithium-ion battery electrolytes, making them difficult to apply to this purpose. Furthermore, regarding fluoropolyether-based curable compositions and their cured products containing fluorine-containing organohydrogen silane compounds that do not contain siloxane bonds and have two or more hydrogen atoms directly bonded to silicon atoms in one molecule, there is no knowledge regarding their durability against lithium-ion battery electrolytes, and it was unclear whether they could be applied to this purpose. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 8-199070 [Patent Document 2] Japanese Patent Publication No. 2011-201940 [Patent Document 3] Japanese Patent Application Publication No. 9-95615 [Patent Document 4] Japanese Patent Publication No. 2011-219692 [Patent Document 5] Japanese Patent Publication No. 2002-012769 [Overview of the project] [Problems that the invention aims to solve]

[0007] The present invention has been made in view of the above circumstances, and provides a fluoropolyether-based curable composition that has durability against hydrofluoric acid and electrolytes for lithium-ion batteries, and provides a cured product that has good release properties without uncured areas due to the low compatibility of the constituent components, and a cured product of the composition, and a cured product having the cured product Lithium-ion battery The purpose is to provide. [Means for solving the problem]

[0008] The present inventors conducted diligent research to solve the above problems and found that when a fluorine-containing organohydrogen silane compound, obtained by introducing a compound having a monovalent perfluoropolyether group and an alkenyl group into an organohydrogen silane compound having three or more hydrosilyl groups of a predetermined structure, is used as a curing agent for a fluoropolyether-based curable composition, it exhibits high compatibility with the base oil, which is a perfluoropolyether compound having an alkenyl group. Furthermore, they found that the cured product obtained by curing a fluoropolyether-based curable composition by adding the fluorine-containing organohydrogen silane compound exhibits durability against hydrofluoric acid and electrolytes for lithium-ion batteries, has no uncured areas on the surface, and has good release properties, leading to the present invention.

[0009] Accordingly, the present invention provides the following fluoropolyether-based curable composition, a cured product obtained from the curable composition, and a lithium-ion battery containing the cured product. [1] (A) Perfluoropolyether compound having two or more alkenyl groups in one molecule: 100 parts by mass, (B) A fluorine-containing organohydrogen silane compound represented by the following general formula (1) and having two or more hydrosilyl groups: (A) an amount such that the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 2.5 moles per mole of alkenyl groups in component (A), and [ka] (In the formula, Rf is a monovalent perfluoropolyether group, and A is the following general formula (7)~(9)) [ka] (In the formula, X 0 X is a hydrogen atom, a methyl group, or an ethyl group. 1 X is independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group. 2R' is a hydrogen atom, methyl group, ethyl group, isopropyl group, or phenyl group; R' is independently a methyl group or an ethyl group; f is an integer from 1 to 6; and t is 0 or 1. Note that bonds marked with an asterisk (*) bond to the Si atom in the above general formula (1), and unmarked bonds bond to Rf. The group is one of the groups represented by , where R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, x is an integer from 1 to 3, and B does not contain a siloxane bond, having two or more diorganohydrosilyl groups when x is 1, and one or more diorganohydrosilyl groups independently when x is 2 or 3, and also having an alkylene group having 1 to 12 carbon atoms where the silicon atoms are unsubstituted and / or fluorine-substituted. A It is a monovalent group forming a sylalkylene structure linked via a sylalkylene group; when x is 1, B has two or more diorganohydrosilyl groups. y is 1 or 2. (C) Platinum group metal catalyst: 0.1 to 2,000 ppm in terms of platinum group metal atoms relative to the mass of component (A) A fluoropolyether-based curable composition for lithium-ion batteries containing the following. [2] (A) The fluoropolyether-based curable composition according to [1], wherein component (A) is a perfluoropolyether compound represented by the following general formula (2). [ka] [In the formula, A 1 This is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may independently contain at least one selected from oxygen, nitrogen, and silicon atoms, and B 1 X 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 if X is a hydrogen atom, then B is bonded to it. 1 It is a carbon atom. Rf 1 It is a divalent perfluoropolyether group. [3] In the component (B), the fluoropolyether-based curable composition according to [1] or [2], wherein Rf in the general formula (1) is a group represented by the following general formula (5). [Chemical formula] (In the formula, D is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms, a, b, c and d are each independently an integer of 0 to 100, 2 ≤ a + b + c + d ≤ 100, and e is an integer of 1 to 3. Each repeating unit shown in the parentheses may be randomly bonded, and these units may be linear or branched.) [4] In the component (B), the fluoropolyether-based curable composition according to any one of [1] to [3], wherein A in the general formula (1) is any one of the groups represented by the following general formulas (7) and (9). [Chemical formula] (In the formula, X 0 is a hydrogen atom, a methyl group or an ethyl group, 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. The bond with * is bonded to the Si atom in the general formula (1), and the bond without a mark indicates bonding to Rf.) [5] In the component (B), the fluoropolyether-based curable composition according to any one of [1] to [4], wherein 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. [6] In the component (B), the fluoropolyether-based curable composition according to any one of [1] to [5], wherein the silylene structure in the molecular chain between Rf in the general formula (1) and the diorganohydrosilyl group in B is two or more in succession. [7] A fluoropolyether-based curable composition according to any one of [1] to [6], wherein in component (B), B in the above general formula (1) is a group represented by the following general formula (10). [ka] [In the formula, p is an integer from 1 to 6, q is an integer from 0 to 6, r is an integer from 1 to 3, R is the same as above, and E is a hydrogen atom or the following formula] [ka] The group is represented by (wherein R is the same as above, p' is an integer from 1 to 6, and q' is an integer from 0 to 6) (however, when E is a hydrogen atom, r is 1). Each repeating unit shown in parentheses with p, q or p', q' above may be combined randomly. [8] A fluoropolyether-based curable composition according to any one of [1] to [7], wherein component (B) is selected from fluorine-containing organohydrogen silane compounds represented by the following formula. [ka] [ka] [ka] [ka] [ka] (In the formula, b' is an integer between 2 and 100, c''' and d'' are integers between 1 and 99, c'''' + d'' = an integer between 2 and 100, Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group. Each repeating unit shown in parentheses with c''' and d'' may be randomly combined.) [9] A fluoropolyether-based curable composition according to [1], wherein the base oil consists solely of component (A). [ 10 ] [1] ~ [ 9 A cured product obtained from a fluoropolyether-based curable composition described in any of the following. [ 11 ] [ 10 A lithium-ion battery having the cured material described in [ ]. [ 12 ] The cured product is a gasket, packing, protective seal, or coating layer. 11 Lithium-ion batteries as described in [ ]. [Effects of the Invention]

[0010] The fluoropolyether-based curable composition of the present invention contains a fluorine-containing organohydrogen silane compound of a specific structure that exhibits high compatibility with the base oil component (A) above, and therefore does not cause turbidity or thickening of the fluoropolyether-based curable composition. Furthermore, by curing the composition, a fluoropolyether-based cured product can be obtained that has durability against hydrofluoric acid and electrolytes for lithium-ion batteries and does not contain scattered oily uncured portions. Moreover, the fluoropolyether-based curable composition has excellent heat resistance, chemical resistance, and solvent resistance comparable to fluoropolyether-based cured products obtained from fluoropolyether-based curable compositions described in Patent Documents 1 to 5. [Modes for carrying out the invention]

[0011] The present invention will be described in more detail below. [(A) component] 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 shown in general formula (2) described later, and acts as the main component (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 repeating 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 polystyrene terms in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as the developing solvent. Furthermore, the number-average degree of polymerization (or number-average molecular weight) of the perfluoropolyether compound described later is 19 It can also be calculated from F-NMR (the same applies below).

[0013] Component (A) is preferably a perfluoropolyether compound having the structure shown in the following general formula (2). [ka] [In the formula, A 1 This is a divalent organic group having 1 to 20 carbon atoms, which may independently contain at least one selected from oxygen, nitrogen, and silicon atoms, and B 1 X 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 if X is a hydrogen atom, then B is bonded to it. 1 It is a carbon atom. Rf 1 It is a divalent perfluoropolyether group.

[0014] In the above general formula (2), A 1A is independently a divalent organic group having 1 to 20 carbon atoms, which may contain at least one selected from oxygen atoms, nitrogen atoms, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one selected from oxygen atoms, nitrogen atoms, and silicon atoms. 1 As for, -(CH2) f -*, -OCH2-*, -(CH2) f OCH2-*, -(CH2) f -NX 2 -CO-*, -(CH2) f -O-CO-* is preferably one of the groups selected from the general formulas (3) and (4) below. Note that the bond marked with * is Rf 1 It combines with the unmarked joint B 1 This indicates that it will combine with [another entity]. [ka] (In the formula, X 1 X is independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group. 2 (where f is a hydrogen atom, methyl group, ethyl group, isopropyl group, or phenyl group, and f is an integer from 1 to 6.)

[0015] A 1 Examples include groups represented by the following general formulas (3A), (3B), (3C), (3D), (4A), (4B), and (4C), with groups represented by general formulas (3A) or (4A) being preferred. Note that bonds marked with an asterisk (*) are Rf 1 It combines with the unmarked joint B 1 This indicates that it bonds with [another group]. Also, Me is a methyl group and Et is an ethyl group. [ka]

[0016] In the above general formula (2), B 1 It 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 X atoms in the molecule (i.e., three at each end of the molecular chain), at least two (particularly, at least one of the three X atoms at each end of the molecular chain) are alkenyl groups. Preferably, the alkenyl group has 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and has a CH2=CH- structure at its terminal. Examples include vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, etc., with vinyl groups and allyl groups being preferred. If X is not an alkenyl group, B 1 When it is a carbon atom, it becomes either a hydrogen atom or a methyl group, B 1 When it is a silicon atom, it becomes a methyl group, forming a structure.

[0017] In the above general formula (2), Rf 1 is a divalent perfluoropolyether group, -C g F 2g This includes a repeating unit of O- (where g is an integer from 1 to 6), such as those represented by the following formula (11). -(C g F 2g O) h - (11) (In the formula, g is an integer between 1 and 6, and h is an integer between 5 and 600, preferably between 10 and 400, and more preferably between 30 and 200.)

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

[0019] Among these, the unit expressed by the following formula is particularly preferred. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O-

[0020] Furthermore, the repeating units in the above-mentioned divalent perfluoropolyether group may consist of one of these types alone, or a combination of two or more types.

[0021] Furthermore, the above-mentioned divalent perfluoropolyether group preferably contains the structure of the following formula. [ka] (In the formula, G is a fluorine atom or a trifluoromethyl group, p1, q1 and r1 are integers satisfying p1≧0, q1≧0, 0≦p1+q1≦200, in particular 2≦p1+q1≦150 and 0≦r1≦6 (when p1+q1=0, 1≦r1≦6), and 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, in particular 2≦s1+t1≦150) Each repeating unit shown in parentheses with v1 and w1 is an integer satisfying 0≦u1≦4 and 2≦s1+t1+u1≦150, v1 and w1 are integers satisfying 1≦v1≦100, 1≦w1≦100, and 2≦v1+w1≦200 respectively, z1 is an integer satisfying 1≦z1≦200, k1', a1', and a1'' are integers satisfying 1≦k1'≦3, 1≦a1'≦6, 1≦a1''≦6, and a1'≠a1'' respectively, and z1' is an integer satisfying 1≦z1'≦200. Each repeating unit shown in parentheses with v1 and w1 may be randomly combined.

[0022] In the above general formula (2), Rf 1 A concrete example of this is the one 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' are integers from 1 to 100, and s1' + t1' = integers from 2 to 200. t1'' is an integer from 2 to 100. Each repeating unit shown in parentheses with v1 and w1 may be combined randomly.)

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

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

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

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

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

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

[0029] The perfluoropolyether compound represented by the above general formula (2) is B 1 When carbon atoms are present, those represented by the following formula are preferred. [ka] (v1 and w1 are integers between 1 and 100, and v1 + w1 = an integer between 2 and 200. Each repeating unit shown in parentheses with v1 and w1 can be randomly combined.)

[0030] The amount of alkenyl groups contained in the perfluoropolyether compound of component (A) is preferably 0.002 to 0.3 mol / 100g, and more preferably 0.008 to 0.12 mol / 100g. If the amount of alkenyl groups contained in the perfluoropolyether compound is less than 0.002 mol / 100g, the degree of crosslinking will be insufficient and curing defects may occur, which is undesirable. If the amount of alkenyl groups exceeds 0.3 mol / 100g, the mechanical properties of the cured product as a rubber elastic body may be impaired, which is also undesirable. In the present invention, the amount of alkenyl groups is 1 It can be measured by 1H-NMR (the same applies in the examples).

[0031] The viscosity (at 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, so that the cured product has appropriate physical properties when the fluoropolyether-based curable composition of the present invention is 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, viscosity (at 23°C) can be measured using a rotational viscometer or the like (e.g., BL type, BH type, BS type, cone plate type, rheometer, etc.) (the same applies hereinafter).

[0032] (A) Component may use one of these perfluoropolyether compounds alone or in combination of two or more.

[0033] [(B) Component] Component (B) used in the fluoropolyether-based curable composition of the present invention is a fluorine-containing organohydrogen silane 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 the linkages between silicon atoms consist of a sylalkylene structure (the alkylene groups in the sylalkylene structure may be partially fluorine-substituted fluorine-substituted alkylene groups), and does not contain siloxane bonds. [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 selected from oxygen, nitrogen, 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 having one or more diorganohydrosilyl groups and forming a sylalkylene structure with a linked silicon atom, and when x is 1, B has two or more diorganohydrosilyl groups. y is 1 or 2.)

[0034] In the general formula (1) above, Rf is a monovalent perfluoropolyether group. Rf is introduced to impart compatibility with the base oil in fluoropolyether-based curable compositions (particularly thermosetting fluoropolyether-based compositions). Compared to perfluoroalkyl groups, perfluoropolyether groups have a greater effect in imparting compatibility with the base oil when introduced into organohydrogen silane compounds, and can yield fluoropolyether-based cured products with excellent 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 is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms, a, b, c, and d are each independent integers from 0 to 100, with 2 ≤ a + b + c + d ≤ 100, preferably a is an integer from 0 to 50, b is an integer from 0 to 50, c is an integer from 0 to 50, d is an integer from 0 to 50, with 5 ≤ a + b + c + d ≤ 50, more preferably a is an integer from 0 to 10, b is an integer from 0 to 40, c is an integer from 0 to 30, d is an integer from 0 to 30, with 6 ≤ a + b + c + d ≤ 40, and even more preferably 7 ≤ a + b + c + d ≤ 30, and e is an integer from 1 to 3. Each repeating unit shown in the parentheses above may be randomly linked, and each of 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, and as a perfluorooxyalkyl group having 1 to 6 carbon atoms, C g F 2g+1 It can be represented as O-(where g is an integer from 1 to 6), and specifically, the base can be represented by the following formula. 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 between the fluorine-containing organohydrogen silane compound and the base oil may be low, which is undesirable. On the other hand, if a+b+c+d is greater than 100, the viscosity of the fluorine-containing organohydrogen silane compound becomes high, and at the same time, the viscosity of the thermosetting fluoropolyether composition to which the fluorine-containing organohydrogen silane compound is added also becomes too high, which is undesirable.

[0038] Examples of monovalent perfluoropolyether groups represented by the above general formula (5) include the following: [ka] (In the formula, g is an integer between 1 and 6, c' is an integer between 2 and 100, b' is an integer between 2 and 100, and e' is 2 or 3. c'' and d' are integers between 0 and 100, c'' + d' is an integer between 2 and 100, and a' is an integer between 2 and 100. Each repeating unit shown in parentheses with c'' and d' can be randomly combined.)

[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 oxygen atoms, nitrogen atoms, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one selected from oxygen atoms, nitrogen atoms, and silicon atoms, and is a C1 to C12 alkylene group including a C1 to C12 alkylene group, a C6 to C8 arylene group (for example, a C8 to C20 alkylene-arylene group), and a C1 to C10 alkylene group bonded to each other via a diorganosilylene group. Examples of divalent groups include divalent groups in which an alkylene group having 1 to 10 carbon atoms and an arylene group having 6 to 8 carbon atoms are linked via a diorganosilylene group, and divalent groups having at least one selected from an ether-linked oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond. In particular, it is preferable that the molecular chain contains at least one selected from an ether-linked oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond. When A contains a silicon atom (diorganosilylene group), it is preferable that the silicon atom (diorganosilylene group) and the silicon atom to which A is linked are linked via an alkylene group (preferably an unsubstituted or fluorine-substituted alkylene group having 1 to 12 carbon atoms, more preferably an ethylene group) to form a sylalkylene structure.

[0040] Specifically, A is preferably represented by one of the following general formulas (6) to (9). [ka] (In the formula, X 0 X is a hydrogen atom, a methyl group, or an ethyl group. 1 X is independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group. 2R' is a hydrogen atom, methyl group, ethyl group, isopropyl group, or phenyl group; R' is independently a methyl group or an ethyl group; f is an integer from 1 to 6; and t is 0 or 1. Note that bonds marked with an asterisk (*) bond to the Si atom in the above general formula (1), and unmarked bonds bond to Rf.

[0041] Examples of structures of A represented by the above general formulas (6) to (9) include the following: [ka] [ka] [ka] [ka] (In the formula, Me represents a methyl group and Et represents an ethyl group. Bonds marked with an asterisk (*) are bonded to the Si atom in the general formula (1) above, and bonds without a mark (*) are bonded to Rf.)

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

[0043] In the above general formula (1), B is a monovalent organic group having one or more diorganohydrosilyl groups and forming a sylalkylene structure with the linked silicon atom, that is, when x is 1, it has two or more, preferably 2 to 5, diorganohydrosilyl groups, and when x is 2 or 3, it has one or more, preferably 1 to 3, independently, diorganohydrosilyl groups and forming a sylalkylene structure with the linked silicon atom, and does not contain siloxane bonds. The sylalkylene structure is an alkylene group R having 1 to 12 carbon atoms where the silicon atoms are unsubstituted and / or fluorine-substituted. AIt is preferable that the structure is linked via a . Furthermore, B preferably has one or more silicon atoms, more preferably 1 to 6, and even more preferably 1 to 4. In formula (1), 1 to 3 such B are bonded to the silicon atoms (x is an integer from 1 to 3), and it is preferable that 2 or 3 are bonded (preferably x is 2 or 3).

[0044] Furthermore, the continuous sylalkylene structure in the molecular chain between Rf in the general formula (1) and the diorganohydrosilyl group in B (i.e., -A-Si-, -Si-(CH2) in the formula) y A continuous sylalkylene bond (-Si-R) including -Si- and -Si-B A It is preferable that the number of -Si-)) is two or more, and more preferably two, three or four.

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

[0046] In the above general formula (10), R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, similar to R in the above general formula (1), and among these, methyl, ethyl, propyl, isopropyl, tert-butyl, and phenyl groups 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 tert-butyl group, and Ph is a phenyl group.)

[0048] Examples of fluorine-containing organohydrogen silane compounds represented by the above general formula (1) include the following: [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, b' is an integer between 2 and 100, c''' and d'' are integers between 1 and 99, c'''' + d'' = an integer between 2 and 100, Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group. Each repeating unit shown in parentheses with c''' and d'' may be randomly combined.)

[0049] [Method for producing fluorine-containing organohydrogen silane compounds] A method for producing the fluorine-containing organohydrosilane compound represented by the above general formula (1) of component (B) preferably includes a step of introducing two or more diorganohydrosilyl groups into the fluorine-containing compound in a predetermined linkage structure by a hydrosilylation reaction using, for example, a fluorine-containing compound containing an alkenyl group (vinyl group) represented by the following general formula (1A) and an organohydrosilane compound having at least three diorganohydrosilyl groups represented by the following general formula (1B). [ka] [ka]

[0050] In general formula (1A), A 2 R is a divalent organic group having 1 to 18 carbon atoms, which may contain at least one 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 the explanations 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 from 1 to 3, B is independently a monovalent organic group having one or more diorganohydrosilyl groups and forming a sylalkylene structure with a linked silicon atom, and when x is 1, B has two or more diorganohydrosilyl groups. y is 1 or 2.

[0051] A 2The C1-C18 divalent organic group (preferably a hydrocarbon group) may contain at least one selected from oxygen, nitrogen, and silicon atoms, and may include C1-C10 alkylene groups, C6-C8 arylene groups (for example, C6-C18 alkylene-arylene groups), divalent groups in which a diorganosilylene group is bonded to a C1-C10 alkylene group, divalent groups in which a diorganosilylene group is bonded to an arylene group with 6-C8 carbon atoms, and diorganosilylene groups in which an alkylene group with 1-C10 carbon atoms and an alkylene group with 1-C8 carbon atoms Examples of divalent groups include divalent groups 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 having at least one selected from an ether-bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond in addition to these groups. In particular, it is preferable that the molecular chain contains at least one selected from an ether-bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond.

[0052] A 2 Specifically, it is preferable that it be represented by one of the following general formulas. [ka] [ka] (In the formula, X 0 , X 1 , X 2 ,f is the same as above, and these explanations are for X in equation (1) above. 0 , X 1 , X 2 The explanation is the same as for f. f' is an integer between 0 and 4. Bonds marked with an asterisk (*) bond with the vinyl group in the general formula (1A) above, while unmarked bonds bond with Rf.

[0053] A, represented by the above general formula 2 Examples of such structures include the following: [ka] [ka] [ka] [ka] (In the formula, Me is a methyl group and Et is an ethyl group. Bonds marked with an asterisk (*) are bonded to the vinyl group in the general formula (1A) above, and unmarked bonds are bonded to Rf.)

[0054] The following shows the manufacturing steps (reaction equation) for a preferred method of producing fluorine-containing organohydrogen silane compounds. [ka]

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

[0056] In the above process, a fluorine-containing organohydrosilane compound represented by the above general formula (1) is produced by hydrosilylation reacting a fluorine-containing compound represented by the above general formula (1A), which has an alkenyl group (preferably a vinyl group or an allyl group) at the end of its molecular chain, with an organohydrosilane compound represented by the above general formula (1B), which has at least three diorganohydrosilyl groups in its molecule, in the presence of a metal catalyst (M).

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

[0058] Examples of organohydrosilane compounds represented by the above general formula (1B) and having at least three diorganohydrosilyl groups in the molecule include the following compounds. [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 above general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the end of its molecular chain used is such that the amount of alkenyl group 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 group in the compound represented by the above general formula (1B). If the amount of alkenyl group in the fluorine-containing compound is less than 0.16 equivalents relative to the amount of hydrosilyl group in the compound represented by the above general formula (1B), it is undesirable because it may cause problems such as turbidity or thickening when the resulting fluorine-containing organohydrogen silane compound is added to a fluoropolyether-based curable composition, or because uncured areas may be scattered on the surface of the cured product obtained by thermal curing. Furthermore, if the amount of alkenyl groups in the fluorine-containing compound exceeds 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 organohydrogen silane compound becomes too low, making it difficult for the fluoropolyether-based curable composition to cure, which is undesirable.

[0060] Furthermore, 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 can be suitably used. For example, chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes with alcohols or vinylsiloxanes, metallic platinum supported on silica, alumina, carbon, etc., RhCl(PPh3)3, RhCl(CO)(PPh3)2, Ru3(CO) 12 Examples include IrCl(CO)(PPh3)2 and Pd(PPh3)4. In the above formula, Ph represents a phenyl group. Among these, platinum compounds are particularly preferred.

[0061] When using these catalysts, if they are solid catalysts, they can be used in solid form, but to allow the reaction to proceed more rapidly, it is preferable to use the metal catalyst dissolved in a suitable solvent. When adding, it is desirable to add them dropwise after confirming that the system in which the fluorine-containing compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl group or allyl group) at the end of the molecular chain, or the organohydrosilane compound represented by the above general formula (1B) and having at least three diorganohydrosilyl groups in the molecule coexists has been heated to a predetermined temperature. The predetermined temperature is preferably 50°C or higher, and more preferably 65°C or higher.

[0062] When a fluorine-containing compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl group or allyl group) at the end of its molecular chain, or an organohydrosilane compound represented by the above general formula (1B) and having at least three diorganohydrosilyl groups in its molecule, is in a solid state, or when these compounds do not dissolve in each other, they may be dissolved in a small amount of organic solvent before adding M (metal catalyst). Examples of usable solvents include benzene, toluene, xylene, and 1,3-bistrifluoromethylbenzene, with 1,3-bistrifluoromethylbenzene being preferred.

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

[0064] The amount of component (B) is such that, for every mole of alkenyl groups such as vinyl groups and allyl groups in component (A), there are 0.1 to 2.5 moles, preferably 0.2 to 2 moles, of hydrogen atoms (hydrosilyl groups, i.e., Si-H groups) bonded to silicon atoms in component (B). If there are too few hydrosilyl groups, the degree of crosslinking will be insufficient, resulting in no cured product being obtained. If there are too many, foaming will occur during curing.

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

[0066] Component (B) may consist of one of these fluorine-containing organohydrogen silane compounds alone, or two or more may be used in combination.

[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 reaction catalyst that promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B) and the optional components such as adhesion improvers and adhesion promoters described later. Since this hydrosilylation reaction catalyst is generally a compound of a precious metal and is expensive, platinum or platinum compounds, which are relatively easy to obtain, 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. Besides platinum compounds, rhodium, ruthenium, iridium, and palladium-based compounds are also known as platinum group metal catalysts, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO). 12 Examples include IrCl(CO)(PPh3)2 and Pd(PPh3)4. In the above formula, Ph represents a phenyl group.

[0069] When using these catalysts, if they are solid catalysts, they can be used in solid form. However, to obtain a more uniform cured product, it is preferable to dissolve chloroplatinic acid or the complex in a suitable solvent and make it compatible with the perfluoropolyether compound of component (A).

[0070] The amount of component (C) used may be a catalytic amount, but it is preferable to blend it at a concentration of 0.1 to 1,000 ppm (in terms of platinum group metal atoms) relative to the mass of component (A), and more preferably at 1 to 500 ppm. Component (C) can be used alone or in combination of two or more types.

[0071] [Other ingredients] In the fluoropolyether-based curable composition of the present invention, in order to enhance its practicality, various additives such as adhesion improvers (adhesion imparters), plasticizers, viscosity modifiers, flexibility imparters, hydrosilylation reaction catalyst control agents, inorganic fillers, adhesion promoters, and silane coupling agents may be added as needed, in addition to the components (A) to (C) above. The amount of these additives added is arbitrary, as long as it does not impair the objectives of the present invention and does not impair the properties of the composition or the physical properties of the cured product.

[0072] The adhesion enhancer acts as an adhesion enhancer to induce self-adhesion in the fluoropolyether-based curable composition of the present invention when incorporated, and is an organohydrogen polysiloxane compound having one or more hydrogen atoms (Si-H group) bonded to a silicon atom and one or more epoxy groups and / or trialkoxysilyl groups bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in one molecule. Although the adhesion enhancer has a molecular structure corresponding to a fluorine-containing organohydrogen siloxane, making it difficult to maintain long-term self-adhesion to hydrofluoric acid or electrolytes for lithium-ion secondary batteries by using this adhesion enhancer, it is extremely effective in situations requiring initial self-adhesion, such as during the manufacturing process of articles having cured products obtained from the fluoropolyether-based curable composition of the present invention.

[0073] In the above adhesion improver, it is more preferable to have 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, nitrogen, carbon, and silicon atoms in one molecule, particularly bonded to silicon atoms via a divalent linking group containing nitrogen and carbon atoms, or bonded to silicon atoms via a divalent linking group containing nitrogen, carbon, and oxygen atoms. As for such perfluoroalkyl groups, C j F 2j+1 A group represented by -(j is an integer from 1 to 10, preferably from 3 to 7) is an example. Furthermore, examples of monovalent perfluoropolyether groups include those similar to those exemplified by Rf in formula (1) shown in component (B) above. Additionally, as the divalent linking group connecting this perfluoroalkyl group or monovalent perfluoropolyether group to the silicon atom, a divalent organic group having 1 to 20 carbon atoms (preferably a hydrocarbon group) may be used, which may contain at least one selected from oxygen, nitrogen, and silicon atoms.

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

[0075] [ka] (In the formula, R 2 L is an unsubstituted or halogen-substituted monovalent hydrocarbon group. 1 M is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group, 1 The repeating units shown in parentheses above are an epoxy group or trialkoxysilyl group bonded to a silicon atom via 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. Each repeating unit shown in parentheses above may be randomly combined.

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

[0077] The above L 1This is 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 R is a monovalent perfluoropolyether group, the same as Rf in the general formula (1) above, and examples similar to those exemplified by Rf can be given. Z is a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms, which may contain at least one selected from oxygen, nitrogen, 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- The following groups are examples of groups represented by the following formulas, with -(CH2)3OCH2-* and -(CH2)3-NH-CO-* being preferred. Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Ph' represents a phenylene group. Furthermore, bonds marked with an asterisk (*) indicate bonding with a monovalent perfluoropolyether group, while bonds without an asterisk (*) indicate bonding with a silicon atom in the organohydrogen polysiloxane. [ka]

[0079] The above M1 This refers to an epoxy group or trialkoxysilyl group bonded to a silicon atom via a carbon atom and an oxygen atom, and specifically, the following groups can be listed.

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

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

[0082] [ka] (In the formula, R 6 R is a hydrogen atom or a methyl group, 7 (where l independently represents a monovalent hydrocarbon group with 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms (such as alkyl groups like methyl, ethyl, propyl, and butyl groups), and l represents an integer from 2 to 10.)

[0083] Organohydrogen polysiloxane compounds used as adhesion improvers can be obtained by partially adding a compound containing an aliphatic unsaturated group such as a vinyl group or an allyl group and an epoxy group and / or a trialkoxysilyl group, to an organohydrogen polysiloxane having three or more hydrogen atoms (Si-H groups) bonded to a silicon atom in one molecule, according to a conventional method, and optionally a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or perfluorooxyalkyl group. The number of aliphatic unsaturated groups must be less than the number of Si-H groups.

[0084] In the production of organohydrogen polysiloxane compounds used as adhesion improvers, the target substance may be isolated after the reaction is complete, or a mixture from which unreacted material and the addition reaction catalyst have been removed may be used.

[0085] Examples of organohydrogen polysiloxane compounds used as adhesion enhancers include those shown in the following structural formulas. These compounds may be used individually or in combination of two or more. In the following formulas, Me represents a methyl group.

[0086] [ka] (In the formula, x2' = 2 or 3, and b1' = an integer between 2 and 20. Each repeating unit shown in parentheses may be combined randomly.)

[0087] [ka] (In the formula, x2' = 2 or 3, and b1' = an integer between 2 and 20. Each repeating unit shown in parentheses may be combined randomly.)

[0088] [ka] (In the formula, x2'' = 1 or 2, and b1' = an integer between 2 and 20. Each repeating unit shown in parentheses may be randomly combined.)

[0089] [ka] (In the formula, z2' = 2 or 3, and b1' = an integer between 2 and 20. Each repeating unit shown in parentheses may be randomly combined.)

[0090] [ka] (In the formula, y2' = 2 or 3, and b1' = an integer between 2 and 20. Each repeating unit shown in parentheses may be randomly combined.)

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

[0092] As plasticizers, viscosity modifiers, and flexibility imparters, polyfluoromonoalkenyl compounds represented by the following general formula (12) and / or polyfluoro compounds 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 having 1 to 20 carbon atoms (preferably a hydrocarbon group) which may contain at least one selected from oxygen, nitrogen, and silicon atoms, and p2 is 0 or 1, and Rf 3 This 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 component (A) to be used 1 is smaller than the molecular weight of.)]

[0094] Y 1 -O-(CF2CF2CF2O) c2 -Y 1 (13) [wherein, Y 1 is independently a group represented 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 component (A) to be used 1 is smaller than the molecular weight of.)]

[0095] Y 2 -O-(CF2O) d2 (CF2CF2O) e2 -Y 2 (14) (wherein, Y 2 is the same as the above Y 1 , d2 and e2 are each an integer of 1 to 200, and Rf in formula (2) in component (A) to be used 1 is smaller than the molecular weight of. Each repeating unit shown in the above ( ) may be randomly bonded.)]

[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 selected from an oxygen atom, a nitrogen atom and a silicon atom. In addition to those similar to Z (divalent linking group) in the above L 1 structure, the following can be exemplified (in the following exemplified formulas of and Z, the bond with * indicates bonding with Rf 3 , and the bond without * indicates bonding with a carbon atom. Me represents a methyl group.)]

Chemical formula

[0097] Specific examples of polyfluoromonoalkenyl compounds represented by the above general formula (12) include the following. Note that f2 below 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 the following c2, d2, e2 and the sum of d2 and e2 satisfy the above requirements. CF3O-(CF2CF2CF2O) c2 -CF2CF3 CF3-O-(OCF2) d2 (OCF2CF2) e2 -CF3

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

[0101] Furthermore, examples of control agents for the hydrosilylation reaction catalyst include acetylene alcohols such as ethynylcyclohexanol (also known as 1-ethynyl-1-hydroxycyclohexane), 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol; reaction products of chlorosilanes having the above-mentioned monovalent fluorine substituents and acetylene alcohols; 3-methyl-3-penten-1-yine, 3,5-dimethyl-3-hexen-1-yine, triallyl isocyanurate, etc.; or polyvinylsiloxanes, organophosphorus compounds, etc. The addition of these agents can appropriately maintain curing reactivity and storage stability. The amount of the control agent is arbitrary within the range that can impart the desired curing properties and storage stability.

[0102] As inorganic fillers, for example, 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, or various surface-treated silica powders obtained by hydrophobizing the untreated surface of the silica powder with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, etc., reinforcing or semi-reinforcing fillers such as quartz powder, fused quartz powder, diatomaceous earth, and calcium carbonate, inorganic pigments such as titanium dioxide, iron oxide, carbon black, and cobalt aluminate, heat resistance improvers such as titanium dioxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate, thermal conductivity imparters such as alumina, boron nitride, silicon carbide, and metal powders, and conductivity imparters such as carbon black, silver powder, and conductive zinc oxide can be added.

[0103] The adhesion promoter, when included with the adhesion enhancer, is intended to improve the adhesion-imparting ability of the adhesion enhancer 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 suitably used.

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

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

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

[0107] Furthermore, in equation (15) above, R 8 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and the above R 2 Similar groups can be mentioned, with methyl and ethyl groups being preferred.

[0108] Furthermore, in formula (15) above, J is a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group, and specifically, a group represented by the following general formula can be mentioned. [ka]

[0109] In the above formula, R 9 This is a divalent hydrocarbon group having 2 to 15 carbon atoms, specifically including ethylene, propylene, and butylene groups, with propylene being preferred.

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

[0111] Examples of cyclic organopolysiloxanes represented by the above 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 between 2 and 20.) [ka] (In the formula, v2' = 2 or 3, and b2' = an integer between 2 and 20.)

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

[0113] When an adhesion promoter is included, the amount 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 is 0.005 to 0.5 moles, and particularly 0.05 to 0.1 moles, per mole of alkenyl groups in component (A). Furthermore, 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) per mole of alkenyl groups in component (A) is 0.1 to 2.5 moles, and more preferably 0.2 to 2 moles.

[0114] [Method for producing a 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 components together. Specifically, the fluoropolyether-based curable composition of the present invention can be produced by uniformly mixing the above components (A) to (C) and other optional components using a mixing device such as a planetary mixer, Ross mixer, or Hobart mixer, and, if necessary, a kneading device such as a kneader or a three-roll mixer. Alternatively, the composition may consist of two components that 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 the catalyst of component (C), but heating is often performed to accelerate the curing. In particular, in order to exhibit good adhesion to various substrates, it is preferable to cure at 60°C or higher, preferably at 100 to 200°C for about several minutes to several hours.

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

[0117] The fluoropolyether-based curable composition of the present invention is preferably used as electrical and electronic components for automobiles, chemical plants, semiconductor manufacturing lines, analytical and physicochemical instruments, residential environments, communication equipment, communication facilities, aircraft, railway vehicles, portable devices, power storage devices, robots, or lithium ion batteries. In particular, electrical and electronic components using the cured product of the fluoropolyether-based curable composition of the present invention as a gasket, packing, protective seal, or coating layer are preferable.

Examples

[0118] Hereinafter, synthesis examples, examples, and comparative examples will be shown to specifically explain the present invention, but the present invention is not limited to the following examples. In the following examples, Me in the formula represents a methyl group, and parts represent parts by mass. The number average molecular weight was determined as the number average molecular weight in terms of polystyrene in 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) represents the value measured in accordance with the method using a rotational viscometer in the viscosity test defined in JIS K6249.

[0119] ·Synthesis of fluorine-containing organohydrogen silane compound [Synthesis Example 1] In a 1 L flask, add the organohydrogen silane compound represented by the following formula (16) (hydrosilyl group content 0.616 mol / 100 g) [ka] 150g and the compound represented by the following formula (17) (vinyl group content 0.0681 mol / 100g) [ka] 339g of 1,3-bistrifluoromethylbenzene and 91g of bistrifluoromethylbenzene were added, and the mixture was purged with nitrogen. After raising the temperature to 70°C, 0.16 g of a toluene solution of (C1) platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass) was added dropwise, and the mixture was 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), stirred with 9.10 g of activated carbon (trade name Shirasagi AS, manufactured by Osaka Gas Chemical Co., Ltd.) for 1 hour, and then filtered. Activated carbon (9.10 g) was added to the resulting solution, stirred for 1 hour, and then filtered. After extracting the main component from the obtained solution by preparative liquid chromatography, the compound represented by the following formula (18) (hydrosilyl group content 0.143 mol / 100g) was obtained by reducing the pressure. [ka] 376g of the obtained product was obtained. 1 The following signals were observed in the 1H-NMR spectrum: δ7.86~6.55 (m, 4H), 4.38~3.64 (m, 3H), 3.15 (s, 3H), 2.46~1.48 (br, 4H), and 1.18~-0.91 (m, 52H), confirming the formation of the compound represented by formula (18) above.

[0120] [Synthesis Example 2] Instead of the compound represented by formula (17) above, use the compound represented by formula (19) below (vinyl group content 0.0228 mol / 100 g) [ka] Except for using 1,012 g of [the compound], the procedure was carried out in the same manner as in Synthesis Example 1, and the compound represented by the following formula (20) (amount of hydrosilyl group: 0.0682 mol / 100 g) was obtained. [ka] 741g of the obtained product was obtained. 1 The following signals were observed in the 1H-NMR spectrum: δ7.68~6.36 (m, 4H), 4.21~3.44 (s, 3H), 3.03 (s, 3H), 2.29~1.41 (br, 4H), and 1.13~-0.98 (m, 52H), confirming the formation of the compound represented by formula (20) above.

[0121] [Synthesis Example 3] Instead of the compound represented by formula (16) above, use the compound represented by formula (21) below (hydrosilyl group amount 1.09 mol / 100 g) [ka] Except for using 85g of [the compound], the procedure was carried out in the same manner as in Synthesis Example 1, and the compound represented by the following formula (22) (amount of hydrosilyl group: 0.247 mol / 100g) was obtained. [ka] 323g of the obtained product was obtained. 1 The following signals were observed in the 1H-NMR spectrum: δ7.85~6.55 (m, 4H), 4.29~3.51 (m, 5H), 3.15 (s, 3H), and 1.23~-0.91 (m, 62H), confirming the formation of the compound represented by formula (22) above.

[0122] [Synthesis Example 4] Instead of the compound represented by formula (17) above, use the compound represented by formula (23) below (vinyl group content 0.0873 mol / 100g) [ka] (Average of m+n = 12, m:n = 0.98:1) The same operations as in Synthesis Example 1 were carried out except that 264 g was used, and a compound represented by the following formula (24) (amount of hydrosilyl group: 0.169 mol / 100 g)

Chemical formula

[0123] <Preparation of fluoropolyether-based curable composition, confirmation of compatibility between component (B) and component (A) (base oil)> [Example 1] To 100 parts of a polymer represented by the following formula (25) (number average molecular weight 15,550, viscosity 10,900 mPa·s, amount of vinyl group 0.012 mol / 100 g), 0.1 part of a toluene solution of a platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), 0.07 part of a compound represented by the following formula (26), and 9.74 parts of a compound represented by the following formula (18) obtained in Synthesis Example 1 (amount of hydrosilyl group 0.143 mol / 100 g) were added and mixed to prepare a curable composition, which was obtained as a transparent oil. From this, it was shown that the compatibility between component (B1) and component (A1) is high.

Chemical formula

Chemical formula

Chemical formula

[0124] [Example 2] In Example 1, instead of (A1) the polymer represented by formula (25) above, 100 parts of (A2) the polymer represented by formula (27) below (number average molecular weight 15,630, viscosity 11,000 mPa·s, vinyl group content 0.012 mol / 100g) were used, and the curable composition was prepared in the same manner as in Example 1, and a transparent oil was obtained. This indicates that component (B1) and component (A2) have high compatibility. [ka] (In the formula, m and n are integers greater than or equal to 1, and the average value of m + n is 90.)

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

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

[0127] [Example 5] In Example 1, instead of (B1) the compound represented by formula (18) above, 5.73 parts of (B3) the compound represented by formula (22) below obtained in Synthesis Example 3 (hydrosilyl group amount: 0.247 mol / 100 g) were used, and the curable composition was prepared in the same manner as in Example 1, and a transparent oil was obtained. This indicates that component (B3) and component (A1) have high compatibility. [ka]

[0128] [Example 6] In Example 1, instead of (B1) the compound represented by formula (18) above, 8.24 parts of (B4) the compound represented by formula (24) below obtained in Synthesis Example 4 (hydrosilyl group amount: 0.169 mol / 100 g) were used, and the curable composition was prepared in the same manner as in Example 1, and a transparent oil was obtained. This indicates that component (B4) and component (A1) have high compatibility. [ka] (m:n=0.98:1, mean of m+n=12)

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

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

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

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

[0133] <Confirmation of the presence or absence of oily components (uncured areas) on the surface of fluoropolyether-based cured products, and evaluation of the release properties of the cured products> The fluoropolyether-based curable compositions prepared in Examples 1-7 and Comparative Examples 1-3 were poured into a 2mm thick stainless steel mold placed on a Teflon (registered trademark, hereinafter the same) sheet, sandwiched between another Teflon sheet, and then press-cured at 150°C for 10 minutes. After press-curing, the release properties of the fluoropolyether-based cured product obtained by removing the 2mm thick stainless steel mold and the residual oily components on the surface of the cured product were evaluated according to the following evaluation criteria. The results, along with the appearance of the fluoropolyether-based curable compositions, are shown in Table 1. [Evaluation Criteria] ○: The hardened material could be easily peeled off the Teflon sheet without damaging it, and no oily residue was observed on the surface of the peeled-off hardened material. ×: It was difficult to peel the cured material from the Teflon sheet without damaging it, and oily residue was observed on the surface of the peeled-off cured material.

[0134] [Table 1]

[0135] In Examples 1-7 and Comparative Example 3, no uncured oily components were observed on the surface of the cured fluoropolyether cured products obtained from the fluoropolyether curable compositions. This is because component (B) in the fluoropolyether curable compositions of Examples 1-7 and Comparative Example 3 showed high compatibility with component (A), resulting in almost all of component (B) and component (A) reacting. Furthermore, the cured products could be easily peeled off the Teflon sheet after press curing, confirming that there were no problems with release properties. On the other hand, uncured oily components were observed on the surface of the fluoropolyether cured products obtained from the fluoropolyether curable compositions of Comparative Examples 1 and 2. This is thought to be because components (B6) and (B7) had poor compatibility with component (A), resulting in insufficient reaction with component (A) during thermal curing, leaving unreacted material as oily components on the surface of the cured fluoropolyether products. Furthermore, the press curing process caused the cured material to adhere to the Teflon sheet, resulting in poor release properties, such as the material breaking or chipping when peeled off the Teflon sheet.

[0136] The fluoropolyether-based cured products obtained above were subjected to post-curing 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 1-7 and Comparative Examples 1-3 were evaluated in accordance with JIS K 6249. Next, the fluoropolyether cured products obtained from the fluoropolyether curable compositions of Examples 1-7 and Comparative Examples 1-3 were left in an oven at 150°C for 7 days. The physical properties of the cured products were then evaluated in accordance with JIS K 6249, and the change in hardness, tensile strength (%), and elongation at break (%) were calculated using the following formulas. The results are shown in Table 2.

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

[0139] [Table 2]

[0140] <Chemical resistance> The fluoropolyether cured products obtained from the fluoropolyether curable compositions of Examples 1-7 and Comparative Examples 1-3 were immersed in concentrated hydrochloric acid, concentrated sulfuric acid, concentrated hydrofluoric acid, trifluoroacetic acid, and 40% by mass KOH (potassium hydroxide) aqueous solutions at 20°C for 3 days, and the change in hardness was measured relative to the hardness before immersion. The same formula as used in the heat resistance test was used to calculate the change in hardness. 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 1-7 and Comparative Examples 1 and 2 exhibited excellent durability against all of the above-mentioned chemicals. On the other hand, the cured product obtained from the fluoropolyether-based curable composition of Comparative Example 3 was found to have poor durability against concentrated hydrofluoric acid and trifluoroacetic acid.

[0143] <Solvent resistance> Using fluoropolyether cured products (cured product samples) obtained from the fluoropolyether curable compositions of Examples 1-7 and Comparative Examples 1-3, immersion tests (immersion time: 70 hours) were conducted in various organic solvents shown in Table 4 in accordance with JIS K 6258, and the volume change rate (%) before and after immersion was measured to evaluate 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] The results in Table 4 confirm that the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 exhibited 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 cured products obtained from the fluoropolyether curable compositions of Examples 1-7 and Comparative Examples 1-3 were immersed in lithium-ion battery electrolyte (manufactured by Kishida Chemical Co., Ltd.) at 80°C for 3 days. The degree of deterioration of the cured products was evaluated based on the changes in hardness, stickiness, and appearance of the cured products before and after immersion, according to the evaluation criteria below.

[0147] [Evaluation Criteria] [Hardness] ○: Almost no change in hardness was observed before and after immersion in lithium-ion battery electrolyte. ×: A significant decrease in hardness was observed after immersion in lithium-ion battery electrolyte. [Stickiness] ○: There was no change in the stickiness of the cured surface after immersion in lithium-ion battery electrolyte. ×: Immersion in lithium-ion battery electrolyte caused the surface of the cured material to become sticky. 〔exterior〕 ○: Almost no change in appearance was observed before and after immersion in lithium-ion battery electrolyte. ×: Swelling, deformation, and decomposition of the hardened material were observed upon immersion in lithium-ion battery electrolyte.

[0148] [Table 5]

[0149] The cured products obtained from the fluoropolyether-based curable compositions of Examples 1-7 and Comparative Examples 1 and 2 showed almost no change in hardness, surface stickiness, or appearance before and after immersion in lithium-ion battery electrolyte. This indicates that the above compositions and cured products can be applied to lithium-ion battery applications. 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 lithium-ion battery electrolyte. Furthermore, the cured product easily tore when both ends were pulled.

[0150] The results above demonstrate that the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 exhibit both durability against hydrofluoric acid and electrolytes for lithium-ion batteries, as well as release properties, thus illustrating the effectiveness of the present invention.

Claims

1. (A) Perfluoropolyether compound having two or more alkenyl groups in one molecule: 100 parts by mass, (B) A fluorine-containing organohydrogen silane compound represented by the following general formula (1) and having two or more hydrosilyl groups: (A) an amount such that the amount of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 2.5 moles per mole of alkenyl groups in component (A), and 【Chemistry 1】 (In the formulas, Rf is a monovalent perfluoropolyether group, and A is the following general formula (7) to (9)) 【Chemistry 13】 (In the formula, X 0 X is a hydrogen atom, a methyl group, or an ethyl group. 1 X is independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group. 2 R' is a hydrogen atom, methyl group, ethyl group, isopropyl group, or phenyl group; R' is independently a methyl group or an ethyl group; f is an integer from 1 to 6; and t is 0 or 1. Note that bonds marked with an asterisk (*) bond with the Si atom in the above general formula (1), and unmarked bonds bond with Rf. The group is one of the groups represented by , where R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, x is an integer from 1 to 3, and B does not contain a siloxane bond, having two or more diorganohydrosilyl groups when x is 1, and one or more diorganohydrosilyl groups independently when x is 2 or 3, and also having an alkylene group having 1 to 12 carbon atoms where the silicon atoms are unsubstituted and / or fluorine-substituted. Ａ It is a monovalent group forming a sylalkylene structure linked via a sylalkylene group, and when x is 1, B has two or more diorganohydrosilyl groups. y is 1 or 2. (C) Platinum group metal catalyst: 0.1 to 2,000 ppm in terms of platinum group metal atoms relative to the mass of component (A) A fluoropolyether-based curable composition for lithium-ion batteries containing the following.

2. The fluoropolyether-based curable composition according to claim 1, wherein component (A) is a perfluoropolyether compound represented by the following general formula (2). 【Chemistry 2】 [In the formula, A 1 This is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may independently contain at least one selected from oxygen, nitrogen, and silicon atoms, and B 1 X 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 if X is a hydrogen atom, then B is bonded to it. 1 Rf is a carbon atom. 1 It is a divalent perfluoropolyether group.

3. The fluoropolyether-based curable composition according to claim 1, wherein in component (B), Rf in the above 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 are each independent integers from 0 to 100 such that 2 ≤ a + b + c + d ≤ 100, and e is an integer from 1 to 3. Each repeating unit shown in the parentheses above may be randomly linked, and each of these units may be linear or branched.)

4. The fluoropolyether-based curable composition according to claim 1, wherein in component (B), A in the above general formula (1) is any of the groups represented by the following general formulas (7) and (9). 【Chemistry 4】 (wherein X 0 is a hydrogen atom, a methyl group or an ethyl 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. The bond with an asterisk is bonded to the Si atom in the above general formula (1), and the bond without a mark indicates bonding to Rf.)

5. The fluoropolyether-based curable composition according to claim 1, wherein in component (B), R in the above general formula (1) is any of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group.

6. The fluoropolyether-based curable composition according to claim 1, wherein in component (B), there are two or more consecutive sylalkylene structures in the molecular chain between Rf of the general formula (1) and the diorganohydrosilyl group in B.

7. The fluoropolyether-based curable composition according to claim 1, wherein in component (B), B in the above general formula (1) is a group represented by the following general formula (10). 【Transformation 5】 [In the formula, p is an integer from 1 to 6, q is an integer from 0 to 6, r is an integer from 1 to 3, R is the same as above, and E is a hydrogen atom or the following formula] 【Transformation 6】 The group is represented by the formula (wherein R is the same as above, p' is an integer from 1 to 6, and q' is an integer from 0 to 6) (however, when E is a hydrogen atom, r is 1). Each repeating unit indicated in parentheses with p, q or p', q' above may be randomly combined.

8. The fluoropolyether-based curable composition according to claim 1, wherein component (B) is selected from fluorine-containing organohydrogen silane compounds represented by the following formula. 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 (In the formula, b' is an integer between 2 and 100, c''' and d'' are integers between 1 and 99, c'''' + d'' = an integer between 2 and 100, Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group. Each repeating unit shown in parentheses with c'''' and d'' may be randomly bonded.)

9. The fluoropolyether-based curable composition according to claim 1, wherein the base oil consists solely of component (A).

10. A cured product obtained from a fluoropolyether-based curable composition according to any one of claims 1 to 9.

11. A lithium-ion battery having the cured product described in claim 10.

12. The lithium-ion battery according to claim 11, wherein the cured product is a gasket, packing, protective seal, or coating layer.

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