Fluoropolyether curable components and cured products, as well as electrical and electronic components.

Abstract

The fluorinated polyether curable composition of the present invention comprises the following components: (A) a perfluoropolyether compound having two or more alkenyl groups in one molecule; (B) a fluorinated organic compound having two or more hydrogenated silyl groups as represented by the following general formula (1), (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 two organic hydrogenated silyl groups and forming a silyl group structure with the attached silicon atom, y is 1 or 2); (C) a platinum group metal catalyst that provides a cured product with good release properties, which has durability for electrolytes used in hydrofluoric acid or lithium-ion batteries and does not have uncured areas due to the low compatibility of the constituent components with each other.

Description

Technical Field

[0001] This invention relates to a fluorinated polyether-based curable composition that provides a cured product with good release properties, exhibiting durability to electrolytes for hydrofluoric acid or lithium-ion batteries and without uncured areas due to the low compatibility of the constituent components; and the invention also relates to the cured product of this composition and electrical and electronic components having the cured product. Prior Technology

[0002] Fluorinated polyether curable compositions obtained by the addition reaction of alkenyl groups with hydrogensilyl groups are well known. For example, as a curable composition, a composition is proposed comprising: a fluorinated polyether compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain (hereinafter also referred to as "base oil"); a fluorinated organohydrosiloxane having two or more hydrogen atoms in one molecule that are directly bonded to silicon atoms; and a platinum group metal compound (Patent Document 1: Japanese Patent Application Publication No. 8-199070, Patent Document 2: Japanese Patent Application Publication Nos. 2011-201940). A composition is proposed in which self-adhesion is imparted by adding an organopolysiloxane having hydrogenated silyl groups, epoxy groups, and / or trialkoxysilyl groups as a third component (adhesion enhancer) (Patent Document 3: Japanese Patent Application Publication No. 9-95615, Patent Document 4: Japanese Patent Application Publication No. 2011-219692). This composition can be cured by short-time heat treatment to obtain a cured product (fluoropolyether-based cured product), and because the resulting cured product exhibits excellent solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, and electrical properties, it is suitable for use in various industrial fields requiring such properties.

[0003] Fluorinated polyether-based curable compositions containing fluorinated organohydrosiloxanes with two or more hydrogen atoms directly bonded to silicon atoms per molecule contain siloxane bonds that are unstable in acids, thus failing to perform adequately in applications requiring high levels of acid resistance. In particular, their durability against hydrofluoric acid is low, making them unsuitable for applications such as parts for semiconductor manufacturing equipment. To address this, it is proposed to replace the fluorinated organohydrosiloxane with a fluorinated organohydrosilane compound having two or more hydrogen atoms directly bonded to silicon atoms per molecule but without siloxane bonds, thereby improving the acid resistance of the fluorinated polyether-based cured composition (Patent Document 5: Japanese Patent Application Publication No. 2002-012769).

[0004] On the other hand, the aforementioned fluorinated organohydrosilane compounds tend to have a higher proportion of unfluorinated organic structures in the overall molecule. This is mainly due to the ease of synthesizing fluorinated organohydrosilane compounds. In this case, the short-chain perfluoroalkyl groups have poor compatibility with the base oil. Due to these tendencies, if fluorinated organohydrosilane compounds are added to fluorinated polyether curing compositions, the fluorinated polyether curing compositions may become cloudy and have increased viscosity. Furthermore, oily uncured portions will also be dispersed on the surface of the fluorinated polyether cured product obtained from the fluorinated polyether curing composition. Due to the dispersion of these uncured portions, the release properties of the fluorinated polyether cured product are mostly impaired, and during the manufacturing process of articles containing the cured product, the cured product will not peel off from the parts in the manufacturing equipment, which may cause defects that prevent the manufacturing process from proceeding smoothly, and is therefore undesirable.

[0005] In recent years, due to increasing attention to environmental issues, the development of products using lithium-ion batteries has been actively pursued globally. However, it has been found that fluoropolyether-based curable compositions containing fluorinated organohydrosiloxanes with two or more hydrogen atoms directly bonded to silicon atoms in one molecule, and the curables thereof, have low durability for lithium-ion battery electrolytes, making them unsuitable for this application. Furthermore, regarding fluoropolyether-based curable compositions and curables obtained by replacing the fluorinated organohydrosiloxanes with fluorinated organohydrosiloxane compounds containing two or more hydrogen atoms directly bonded to silicon atoms in one molecule but without siloxane bonds, no insights have been found regarding their durability for lithium-ion battery electrolytes, and it is unclear whether they are suitable for this application. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 8-199070 [Patent Document 2] Japanese Patent Application Publication No. 2011-201940 [Patent Document 3] Japanese Patent Application Publication No. 9-95615 [Patent Document 4] Japanese Patent Application Publication No. 2011-219692 [Patent Document 5] Japanese Patent Application Publication No. 2002-012769 Summary of the Invention

[0007] [The problem that the invention aims to solve]

[0008] The present invention is made in view of this situation and aims to provide a fluoropolyether-based curable composition that provides a cured product with good release properties, which has durability for hydrofluoric acid or lithium-ion battery electrolytes and has no uncured parts due to the low compatibility of the constituent components; and provides a cured product of the composition and electrical and electronic parts having the cured product. [Methods for solving problems]

[0009] Through in-depth research to solve the aforementioned problems, the inventors discovered the following insight: When using a fluorinated organohydrosilane compound obtained by introducing a compound having a monovalent perfluoropolyether group and an alkenyl group into an organohydrosilane compound having three or more hydrogenated silyl groups in a specified structure, as a curing agent for fluorinated polyether curable compositions, a high compatibility is observed with the alkenyl-containing perfluoropolyether compound used as a base oil. Furthermore, it was found that curing the fluorinated polyether curable composition obtained by adding this fluorinated organohydrosilane compound results in a cured product that exhibits durability with hydrofluoric acid or lithium-ion battery electrolytes, and has no uncured portions on the surface, thus providing excellent mold release properties. Therefore, this invention is complete.

[0010] Therefore, the present invention provides the following fluoropolyether-based curable composition, the cured product obtained from the curable composition, and electrical and electronic components comprising the cured product. [1] A fluorinated polyether-based curable composition comprising the following components, (A) Perfluoropolyether compounds having two or more alkenyl groups in one molecule: 100 parts by weight; (B) Fluorinated organosilicon compounds having two or more hydrogenated silyl groups, represented by the following general formula (1): relative to the 1 mol of the alkenyl group in component (A), the amount of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 2.5 mol; and, (C) Platinum group metal catalyst: 0.1~2,000 ppm relative to component (A) in platinum group metal atomic conversion. (In the formula, Rf is a monovalent perfluoropolyether group, A is a divalent organic group with 1 to 20 carbon atoms that may contain at least one of oxygen, nitrogen and silicon atoms, R is a monovalent hydrocarbon group with 1 to 6 carbon atoms, x is an integer from 1 to 3, B is a monovalent organic group that has one or more diorganohydrosilyl groups and forms a silyl group structure with the attached silicon atom, if x is 1, B has two or more diorganohydrosilyl groups, and y is 1 or 2). [2] As in [1], fluorinated polyethers are curable components, wherein component (A) is a perfluoropolyether compound represented by the following general formula (2). [In the formula, A1 is an independent divalent organic group with 1 to 20 carbon atoms, which may contain at least one of oxygen, nitrogen and silicon atoms; B1 is a carbon atom or a silicon atom; X is an independent hydrogen atom, a methyl group or an alkenyl group with 2 to 8 carbon atoms, but at least two of X are alkenyl groups with 2 to 8 carbon atoms; if X is a hydrogen atom, the bonded B1 is a carbon atom; and Rf1 is a divalent perfluoropolyether group]. [3] Fluoropolyether-based curable compositions, such as those in [1] or [2], wherein, in component (B), Rf in the above general formula (1) is a base represented by the following general formula (5), (In the formula, D is a fluorine atom or a perfluorooxyalkyl group with 1 to 6 carbon atoms, a, b, c and d are independent integers from 0 to 100, and 2≦a+b+c+d≦100, e is an integer from 1 to 3, and each repeating unit represented in the parentheses above can be randomly bonded, and each of these units can be linear or branched). [4] As in any of [1] to [3], the fluorinated polyether is a curable composition, wherein in component (B), A in the above general formula (1) is selected from the following groups: alkyl groups having 1 to 12 carbon atoms, alkyl groups containing aryl groups having 6 to 8 carbon atoms, divalent groups formed by alkyl groups bonded to each other through two organosilicon groups, divalent groups formed by alkyl groups and aryl groups bonded to each other through two organosilicon groups, and such groups further having at least one divalent group selected from ether-bonded oxygen atoms, secondary amino groups, tertiary amino groups and amide bonds. [5] As in any of [1] to [4], the fluorinated polyether is a curable composition, wherein, in component (B), A in the above general formula (1) is any one of the bases represented by the following general formulas (6) to (9). (In the formula, X0 is a hydrogen atom, methyl or ethyl, X1 is independently a hydrogen atom, fluorine atom, methyl, ethyl or trifluoromethyl, X2 is a hydrogen atom, methyl, ethyl, isopropyl or phenyl, R' is independently methyl or ethyl, f is an integer from 1 to 6, t is 0 or 1, and the bonded part with * indicates a bond with the Si atom in the above general formula (1), and the unmarked bonded part indicates a bond with Rf). [6] For example, any one of the fluorinated polyethers in [1] to [5] is a curable composition, wherein in component (B), R in the above general formula (1) is any one of methyl, ethyl, isopropyl, tributyl, or phenyl. [7] The fluorinated polyether curing composition of any one of [1] to [6], wherein in component (B), there are two or more silyl groups in the molecular chain between Rf of the above general formula (1) and the diorganohydrosilyl group in B. [8] For example, any of the fluorinated polyethers in [1] to [7] is a curable composition, wherein, in component (B), B in the above general formula (1) is a base represented by the following general formula (10), [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 a base represented by the following formula.] (In the formula, R is the same as above, p' is an integer from 1 to 6, and q' is an integer from 0 to 6) (but, when E is a hydrogen atom, r is 1), and the repeating units represented in the parentheses above p, q or p', q' can be randomly bonded). [9] As in any of [1] to [8], the fluorinated polyether is a curable component, wherein component (B) is selected from fluorinated organic hydrosilane compounds represented by the following formula. (In the formula, b' is an integer from 2 to 100, c''' and d'' are integers from 1 to 99 respectively, and c'''+d''=2 to 100, Me is methyl, Et is ethyl, Ph is phenyl, and the repeating units represented in the parentheses with c''' and d'' can be randomly bonded).

[10] A cured material obtained from any one of the fluorinated polyether curing components in [1] to [9].

[11] An electrical and electronic component having a hardened material as described in

[10] .

[12] Electrical and electronic components, such as

[11] , wherein the hardened material is a sealing gasket, a sealing pad, a protective sealant, or a coating layer.

[13] Electrical and electronic components such as

[11] or

[12] are used in automobiles, chemical plants, semiconductor manufacturing lines, analytical and physical chemical machinery, living environments, communication machines, communication equipment, aircraft, railway vehicles, portable machines, power storage devices, robots, or lithium-ion batteries. [The effects of the invention]

[0011] The fluoropolyether-based curable composition of the present invention contains a fluorinated organohydrosilane compound with a specific structure that exhibits high compatibility with the aforementioned component (A) as the base oil, thus preventing turbidity or thickening of the fluoropolyether-based curable composition. Furthermore, by curing this composition, a fluoropolyether-based cured product exhibiting durability against hydrofluoric acid and lithium-ion battery electrolytes, and without any oily, uncured portion, can be obtained. Moreover, this fluoropolyether-based curable composition possesses excellent heat resistance, chemical resistance, and solvent resistance comparable to fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions described in Patent Documents 1-5. Implementation

[0012] [Optimal Form of Invention Implementation]

[0013] The present invention will now be described in detail. [(A) ingredient] The perfluoropolyether compound of component (A) used in the fluoropolyether curable composition of the present invention has at least two alkenyl groups in one molecule, preferably having a divalent perfluoropolyether structure in the main chain as represented by the general formula (2) described below, and functions as a main agent (base oil) in the fluoropolyether curable composition of the present invention.

[0014] In this invention, the degree of polymerization (or molecular weight) of polyfluorinated compounds, reflecting the number of repeating perfluoroalkyl units constituting the perfluoropolyether structure of the main chain, can be obtained, for example, in gel permeation chromatography (GPC) analysis using a fluorinated solvent as the developing solvent, by converting the result to polystyrene using the number average degree of polymerization (or number average molecular weight). Furthermore, the number average degree of polymerization (or number average molecular weight) of the perfluoropolyether compounds described later can also be calculated from 19F-NMR (the same applies hereinafter).

[0015] (A) The component is preferably a perfluoropolyether compound having the structure represented by the following general formula (2). [In the formula, A1 is an independent divalent organic group with 1 to 20 carbon atoms, which may contain at least one of oxygen, nitrogen and silicon atoms; B1 is a carbon atom or a silicon atom; X is an independent hydrogen atom, a methyl group or an alkenyl group with 2 to 8 carbon atoms, but at least two of X are alkenyl groups with 2 to 8 carbon atoms; if X is a hydrogen atom, the bonded B1 is a carbon atom; and Rf1 is a divalent perfluoropolyether group].

[0016] In the above general formula (2), A1 is independently an organic group with a carbon number of 1 to 20, selected from oxygen, nitrogen, and silicon atoms, and preferably contains a hydrocarbon group with a carbon number of 1 to 20, selected from oxygen, nitrogen, and silicon atoms. A1 is composed of a group selected from -(CH2)f-*, -OCH2-*, -(CH2)fOCH2-*, -(CH2)f-NX2-CO-*, -(CH 2) fO-CO-*, any of the bases represented by the following general formulas (3) and (4) is preferred. Also, the bonding part with * indicates a bond with Rf 1, and the unmarked bonding part indicates a bond with B 1. (In the formula, X1 is independently a hydrogen atom, fluorine atom, methyl, ethyl or trifluoromethyl, X2 is a hydrogen atom, methyl, ethyl, isopropyl or phenyl, and f is an integer from 1 to 6).

[0017] Examples of A1 include -CH 2-*, -CH 2CH 2CH 2-*, -OCH 2-*, -CH 2OCH 2-*, and -(CH 2) 2OCH 2-*. -(CH 2) 3OCH 2-*, -CH 2-NH-CO-*, -CH 2-N(Me)-CО-*, -CH 2CH 2-NH-CО-*, -(CH 2) 3-NH-CO-*, -(CH 2) 3-N(Me)-CO-*, -(CH 2) 3-N(Et)-CO-*, -(CH 2) 3-N(CH(Me) 2)-CO-*, -(CH 2) 3-O-CO-*, and the groups represented by the following general formulas (3A), (3B), (3C), (3D), (4A), (4B), and (4C), wherein the groups represented by general formula (3A) or (4A) are preferred. Furthermore, the bonding portion with * indicates a bond with Rf 1, and the unlabeled bonding portion indicates a bond with B 1. Also, Me is methyl, and Et is ethyl.

[0018] In the general formula (2) above, B1 is a carbon atom or a silicon atom. Furthermore, X can be independently a hydrogen atom, a methyl group, or an alkenyl group with 2 to 8 carbon atoms, but at least two of X are alkenyl groups with 2 to 8 carbon atoms. Of the six X groups present in the molecule (i.e., three at each end of the molecular chain), at least two (especially at least one of the three X groups at each end of the molecular chain) are alkenyl groups. It is preferable that the alkenyl group has 2 to 8 carbon atoms (especially 2 to 6) and has a CH 2=CH- structure at the end. Examples include vinyl, allyl, propenyl, isopropenyl, butenyl, and hexenyl, with vinyl and allyl being preferred. If X is not an alkenyl group, when B1 is a carbon atom, it becomes either a hydrogen atom or a methyl group; when B1 is a silicon atom, it becomes a methyl group.

[0019] In the above general formula (2), Rf 1 is a divalent perfluoropolyether group and contains a repeating unit of -C gF 2gO- (where g is an integer from 1 to 6), such as that represented by the following formula (11). (In the formula, g is an integer from 1 to 6, h is an integer from 5 to 600, preferably an integer from 10 to 400, and even more preferably an integer from 30 to 200).

[0020] As a repeating unit represented by the above formula -C gF 2gO-, examples include units represented by the following formula.

[0021] Of these, the units represented by the following formula are particularly suitable.

[0022] Furthermore, the repeating units in the aforementioned divalent perfluoropolyether group can be formed by one of these units alone, or by a combination of two or more of them.

[0023] Furthermore, the aforementioned divalent perfluoropolyether system is preferably structured in the manner described below. (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, and especially satisfying 2≦p1+q1≦150 and 0≦R1≦6 (when p1+q1=0, 1≦R1≦6), respectively, 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, and 0≦u1≦6, and especially satisfying 2≦s1+t1≦6.) ≦150, 0≦u1≦4, 2≦s1+t1+u1≦150, v1 and w1 are integers satisfying 1≦v1≦100, 1≦w1≦100, 2≦v1+w1≦200 respectively, z1 is integers satisfying 1≦z1≦200, k1', a1' and a1'' are integers satisfying 1≦k1'≦3, 1≦a1'≦6, 1≦a1''≦6, a1'≠a1'' respectively, z1' is integers satisfying 1≦z1'≦200. The repeating units represented in parentheses around v1 and w1 can be random (linked to a random key).

[0024] In the above general formula (2), as a specific example of Rf 1, the following formula can be used as an example. (In the formula, p1, q1, R1, v1, w1, z1, 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. The repeating units represented in parentheses for v1 and w1 can be randomized.)

[0025] For the perfluoropolyether compound represented by the general formula (2) above, if B1 is a silicon atom, it is particularly suitable to be represented by the following formula: where Me is methyl and Et is ethyl.

[0026] (s1' and t1' are integers from 1 to 100, and s1' + t1' = integers from 2 to 200).

[0027] (s1' and t1' are integers from 1 to 100, and s1' + t1' = integers from 2 to 200).

[0028] (s1' and t1' are integers from 1 to 100, and s1' + t1' = integers from 2 to 200).

[0029] (s1' and t1' are integers from 1 to 100, and s1' + t1' = integers from 2 to 200).

[0030] (s1' and t1' are integers from 1 to 100, and s1' + t1' = integers from 2 to 200).

[0031] For the perfluoropolyether compound represented by the general formula (2) above, if B1 is a carbon atom, the following formula is suitable. (v1 and w1 are integers from 1 to 100, and v1 + w1 = 2 to 200. The repeating units represented in parentheses around v1 and w1 can be random.)

[0032] (A) The alkenyl content in the perfluoropolyether compound is preferably 0.002~0.3 mol / 100g, more preferably 0.008~0.12 mol / 100g. If the alkenyl content in the perfluoropolyether compound is less than 0.002 mol / 100g, the degree of crosslinking will be insufficient, and there is a possibility of poor curing, which is undesirable. If the alkenyl content exceeds 0.3 mol / 100g, the mechanical properties of the cured material as a rubber elastomer may be impaired, which is also undesirable. In this invention, the alkenyl content can be measured by 1H-NMR (as in the examples).

[0033] (A) The viscosity (23°C) of the perfluoropolyether compound is 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. When the fluoropolyether-based curable composition of the present invention is used in sealing, filling, coating, impregnation, etc., it is preferable to have suitable physical properties even in the cured material. Within this viscosity range, the most suitable viscosity can be selected according to the application. In the present invention, the viscosity (23°C) can be measured using a rotational viscometer or the like (e.g., BL type, BH type, BS type, cone-plate viscometer type, rheometer, etc.) (the same applies below).

[0034] (A) The components may be used alone or in combination of two or more perfluoropolyether compounds.

[0035] [(B) Component] The component (B) used in the fluorinated polyether curable composition of the present invention is a fluorinated organohydrosilane compound having two or more hydrogenated silyl groups, as represented by the following general formula (1). Specifically, it is characterized by having two or more hydrogenated silyl groups, and the silicon atoms are all linked together by a silyl group structure (also, the silyl group in the silyl group structure may be a fluorinated substituted silyl group that is partially substituted with fluorine), but does not contain siloxane bonds. (In the formula, Rf is a monovalent perfluoropolyether group, A is a divalent organic group with 1 to 20 carbon atoms that may contain at least one of oxygen, nitrogen and silicon atoms, R is a monovalent hydrocarbon group with 1 to 6 carbon atoms, x is an integer from 1 to 3, B is a monovalent organic group that has one or more diorganohydrosilyl groups and forms a silyl group structure with the attached silicon atom, if x is 1, B has two or more diorganohydrosilyl groups, and y is 1 or 2).

[0036] In the above general formula (1), Rf is a monovalent perfluoropolyether group. Rf is introduced to impart compatibility with the base oil in fluoropolyether curable compositions (especially thermosetting fluoropolyether compositions). Compared to perfluoroalkyl groups, introducing perfluoropolyether groups into organohydrosilane compounds has a greater effect on imparting compatibility with the base oil, thus providing fluoropolyether curables with good properties.

[0037] In particular, the Rf group in the above general formula (1) is preferably a monovalent perfluoropolyether group represented by the following general formula (5). (In the formula, D is a fluorine atom or a perfluorooxyalkyl group with 1 to 6 carbon atoms, a, b, c and d are each independent integers from 0 to 100, 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, 5≦a+b+c+d≦50, even 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, 6≦a+b+c+d≦40, more preferably 7≦a+b+c+d≦30, e is an integer from 1 to 3, and each repeating unit represented in the parentheses above can be randomly bonded, and each of these units can be linear or branched).

[0038] In the above general formula (5), D is a fluorine atom or a perfluoroalkyl group with 1 to 6 carbon atoms. The perfluoroalkyl group with 1 to 6 carbon atoms is represented by C gF 2g+1O- (g is an integer from 1 to 6). Specifically, the group represented by the following formula can be cited. For D-series systems, fluorine atoms are preferred.

[0039] In the general formula (5) above, if a+b+c+d is less than 2, it is undesirable because the fluorinated organohydrosilane compound has low compatibility with the base oil. On the other hand, if a+b+c+d is greater than 100, it is undesirable because the viscosity of the fluorinated organohydrosilane compound will increase, and the viscosity of the thermosetting fluoropolyether composition containing the fluorinated organohydrosilane compound will also become too high.

[0040] Examples of monovalent perfluoropolyether groups represented by the above general formula (5) include the following. (In the formula, g is an integer from 1 to 6, c' is an integer from 2 to 100, b' is an integer from 2 to 100, and e' is 2 or 3. c'' and d' are integers from 0 to 100, c''+d' is an integer from 2 to 100, and a' is an integer from 2 to 100. The repeating units represented in the parentheses attached to c'' and d' can be randomized).

[0041] In the above general formula (1), A is a divalent organic group having 1 to 20 carbon atoms, which may contain at least one of oxygen, nitrogen, and silicon atoms. Preferably, it is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one of oxygen, nitrogen, and silicon atoms. Examples include: alkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 12 carbon atoms containing aryl groups having 6 to 8 carbon atoms (e.g., cycloalkyl-aryl groups having 8 to 20 carbon atoms), divalent groups having 1 to 10 carbon atoms bonded together by two organosilicon groups, divalent groups having 1 to 10 carbon atoms bonded together by two organosilicon groups, and such groups further having an oxygen atom bonded to an ether, a secondary amino group (imino group), etc. The molecular chain preferably contains at least one divalent group selected from ether-bonded oxygen atoms, secondary amino groups (imino groups), tertiary amino groups (substituted imino groups), and amide bonds. Furthermore, if A contains a silicon atom (diorganosilyl group), it is preferable that the silicon atom (diorganosilyl group) and the silicon atom linked to A are connected through an alkyl group (preferably an unsubstituted or fluorinated alkyl group having 1 to 12 carbon atoms, and more preferably an ethyl group) to form a silylalkyl structure.

[0042] As for A, it is preferred to use any of the following general formulas (6) to (9). (In the formula, X0 is a hydrogen atom, methyl or ethyl, X1 is independently a hydrogen atom, fluorine atom, methyl, ethyl or trifluoromethyl, X2 is a hydrogen atom, methyl, ethyl, isopropyl or phenyl, R' is independently methyl or ethyl, f is an integer from 1 to 6, t is 0 or 1, and the bonded part with * indicates a bond with the Si atom in the above general formula (1), and the unmarked bonded part indicates a bond with Rf).

[0043] Examples of constructs of A represented by the general formulas (6) to (9) above can be given as follows. (In the formula, Me is methyl and Et is ethyl. Also, the bonding part with * indicates the bond with the Si atom in the above general formula (1), and the unmarked bonding part indicates the bond with Rf).

[0044] In the above general formula (1), R is independently a monovalent hydrocarbon group with 1 to 6 carbon atoms, and is preferably methyl, ethyl, isopropyl, tributyl, or phenyl, with methyl or ethyl being even more preferred.

[0045] In the above general formula (1), B is a monovalent organic group with a silylene structure formed by having one or more diorganohydrosilyl groups and the attached silicon atom. That is, if x is 1, B is a monovalent organic group containing silicon with a silylene structure formed by having two or more (preferably two to five) diorganohydrosilyl groups and the attached silicon atom, and does not contain siloxane bonds; if x is 2 or 3, B is a monovalent organic group containing silicon with a silylene structure formed by having one or more (preferably one to three) diorganohydrosilyl groups and the attached silicon atom, and does not contain siloxane bonds. The silicon alkyl group structure is preferably a structure in which silicon atoms are linked to each other by unsubstituted and / or fluorine-substituted alkyl groups RA with 1 to 12 carbon atoms. Furthermore, the B-system is preferably composed of one or more silicon atoms, more preferably one to six, and even more preferably one to four. In formula (1), the B-system typically has one to three silicon atoms bonded to it (x = an integer from 1 to 3), preferably two or three (preferably x is two or three).

[0046] Furthermore, in the molecular chain between the diorganohydrosilyl group in Rf and B of the above general formula (1), the number of consecutive silyl groups (i.e., consecutive silyl groups (-Si-RA-Si-) including -A-Si-, -Si-(CH2)y-Si- and -Si-B in the formula) is preferably two or more, and more preferably two, three or four.

[0047] Series B is preferred as expressed by the following general formula (10). [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 an integer from 0 or 4 to 6; r is an integer from 1 to 3; R is the same as above; E is a hydrogen atom or a base represented by the following formula.] (In the formula, R is the same as above, p' is an integer from 1 to 6, preferably an integer from 1 to 4, q' is an integer from 0 to 6, preferably an integer from 0 or 4 to 6) (However, when E is a hydrogen atom, r is 1), and the repeating units represented in the parentheses above p, q or p', q' can be randomly bonded).

[0048] Similar to R in the above general formula (1), R in the above general formula (10) refers to a monovalent hydrocarbon group with 1 to 6 carbon atoms, wherein methyl, ethyl, propyl, isopropyl, tributyl, and phenyl are particularly preferred.

[0049] Examples of the B series in the above general formula (1) are as follows. (In the formula, Me is methyl, Et is ethyl, iPr is isopropyl, tBu is tributyl, and Ph is phenyl).

[0050] Examples of fluorinated organohydrosilane compounds represented by the above general formula (1) include the following. (In the formula, b' is an integer from 2 to 100, c''' and d'' are integers from 1 to 99 respectively, and c'''+d''=2 to 100, Me is methyl, Et is ethyl, Ph is phenyl, and the repeating units represented in the parentheses with c''' and d'' can be randomly bonded).

[0051] [Manufacturing method of fluorinated organohydrosilane compounds] (B) A preferred method for manufacturing a fluorinated organohydrosilane compound represented by the general formula (1) above includes, for example, the following steps: introducing two or more diorganohydrosilane groups into a fluorinated compound in a specified linked structure by a hydrosilanization reaction of a fluorinated compound containing an alkenyl (vinyl) group represented by the general formula (1A) below with an organohydrosilane compound having at least three diorganohydrosilane groups represented by the general formula (1B).

[0052] In general formula (1A), A2 is a divalent organic group having 1 to 18 carbon atoms, which may contain at least one of oxygen, nitrogen, and silicon atoms. The descriptions of Rf, R, B, y, and x in the above general formulas (1A) and (1B) are the same as those 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 silyl group structure with the attached silicon atom, and if x is 1, B has two or more diorganohydrosilyl groups, and y is 1 or 2.

[0053] A2 is a divalent organic group (preferably a hydrocarbon group) having 1 to 18 carbon atoms, which may contain at least one of oxygen, nitrogen, and silicon atoms. Examples include: alkyl groups having 1 to 10 carbon atoms; alkyl groups having 1 to 10 carbon atoms containing aryl groups having 6 to 8 carbon atoms (e.g., cycloalkyl-aryl groups having 6 to 18 carbon atoms); divalent groups formed by the bonding of two organosilicon groups to alkyl groups having 1 to 10 carbon atoms; divalent groups formed by the bonding of two organosilicon groups to aryl groups having 6 to 8 carbon atoms; and alkyl groups having 1 to 10 carbon atoms and alkyl groups having 1 to 8 carbon atoms. The divalent group formed by the bonding of an alkyl group through two organosilyl groups, the divalent group formed by the bonding of an alkyl group having 1 to 8 carbons and an aryl group having 6 to 8 carbons through two organosilyl groups, and the groups further having at least one divalent group selected from ether-bonded oxygen atoms, secondary amino groups (imino groups), tertiary amino groups (substituted imino groups) and amide bonds, wherein it is preferred that the molecular chain contains at least one divalent group selected from ether-bonded oxygen atoms, secondary amino groups (imino groups), tertiary amino groups (substituted imino groups) and amide bonds.

[0054] As for A2, it is preferred to use any of the following general formulas. (In the formula, X0, X1, X2, and f are the same as above, and their descriptions are the same as those of X0, X1, X2, and f in the above formula (1). f' is an integer from 0 to 4. The bond portion with * indicates the vinyl bond with the above general formula (1A), and the unmarked bond portion indicates the Rf bond).

[0055] Examples of constructs for A 2 as represented by the above general formula can be given as follows. (In the formula, Me is methyl and Et is ethyl. The bonding part with * indicates the vinyl bond with the above general formula (1A), and the unmarked bonding part indicates the Rf bond.)

[0056] The following describes the manufacturing steps (reaction formulas) of a preferred method for manufacturing fluorinated organohydrosilane compounds.

[0057] The descriptions of Rf, A, R, B, y, and x in the reaction formulas shown in the above steps are the same as those in the general formula (1) above. The description of A2 is the same as that in the general formula (1A) above. M is a metal catalyst.

[0058] In the above steps, the fluorinated organohydrosilane compound represented by the above general formula (1) is produced by carrying out a hydrogenation silylation reaction in the presence of a metal catalyst (M) on a fluorinated compound with an alkenyl group (preferably vinyl or allyl) at the end of the molecular chain represented by the above general formula (1A) and an organohydrosilane compound represented by the above general formula (1B) having at least 3 diorganohydrosilyl groups.

[0059] In the above reaction, the fluorinated compound having an alkenyl group (preferably vinyl or allyl) at the end of the molecular chain represented by the above general formula (1A) can be, for example, the following compounds. (In the formula, b' is an integer from 2 to 100, c''' and d'' are integers from 1 to 99 respectively, and c''' + d'' = an integer from 2 to 100, Me is methyl, and Et is ethyl. The repeating units represented in the parentheses of c''' and d'' can be randomly bonded.)

[0060] As an organohydrosilane compound having at least three diorganohydrosilyl groups in the molecule represented by the above general formula (1B), the following compounds may be used, for example. (In the formula, Me is methyl, Et is ethyl, and Ph is phenyl).

[0061] The amount of the fluorinated compound with an alkenyl group (preferably vinyl or allyl) at the end of the molecular chain represented by the above general formula (1A) is 0.16 to 0.30 equivalents, preferably 0.20 to 0.25 equivalents, relative to the amount of hydrogenated silane in the compound represented by the above general formula (1B). If the amount of alkenyl in the fluorinated compound is less than 0.16 equivalents relative to the amount of hydrogenated silane in the compound represented by the above general formula (1B), adding the obtained fluorinated organosilane compound to a fluorinated polyether curable composition may cause turbidity or thickening, and may result in uncured portions being dispersed on the surface of the cured material obtained by heat curing, which is undesirable. Furthermore, if the amount of silyl group in the fluorinated compound is more than 0.30 equivalents relative to the amount of silyl group in the compound represented by the general formula (1A) above, the amount of silyl group in the obtained fluorinated organosilane compound will become too small, making it difficult to cure the fluorinated polyether curable composition, which is undesirable.

[0062] Furthermore, the above reaction steps can be rapidly carried out by adding M (a metal catalyst). Any metal catalyst capable of serving as a catalyst for hydrogenation silanization is acceptable; M is not particularly limited and compounds containing metal atoms such as platinum, rhodium, ruthenium, and palladium are suitable. Examples include platinum chloride or its complexes with olefins such as ethylene, complexes with alcohols or vinyl siloxanes, platinum supported on silicon dioxide, alumina, carbon, etc., RhCl(PPh 3) 3, RhCl(CO)(PPh 3) 2, Ru 3(CO) 12, IRCl(CO)(PPh 3) 2, Pd(PPh 3) 4, etc. Also, in the aforementioned formulas, Ph represents a phenyl group. Platinum compounds are particularly preferred.

[0063] When these are used as catalysts, they can be used in solid form if they are solid catalysts. However, for faster reaction, it is preferable to dissolve the aforementioned metal catalysts in a suitable solvent. When adding the catalyst, it is advisable that the system containing either a fluorinated compound with an alkenyl group (preferably vinyl or allyl) at the end of the molecular chain represented by the above general formula (1A) or an organohydrosilane compound with at least three diorganohydrosilyl groups in the molecule represented by the above general formula (1B) has been heated to a specified temperature before dropping. The specified temperature is preferably 50°C or higher, and more preferably 65°C or higher.

[0064] If the fluorinated compound represented by the general formula (1A) above has an alkenyl group (preferably vinyl or allyl) at the end of the molecular chain, or the organohydrosilane compound represented by the general formula (1B) above has at least three diorganohydrosilyl groups in its molecule, is a solid, or if the compounds are insoluble in each other, then at least a small amount of organic solvent may be dissolved in the solvent before adding M (metal catalyst). Examples of solvents that can be used include benzene, toluene, xylene, and 1,3-bis(trifluoromethylbenzene), with 1,3-bis(trifluoromethylbenzene) being preferred.

[0065] (B) The amount of silane-containing fluorinated organosilane compound is preferably 0.05~0.35 mol / 100g, and even more preferably 0.06~0.30 mol / 100g. In this invention, the amount of silane-containing compound can be measured by 1H-NMR (as in the examples).

[0066] The amount of component (B) mentioned above is 1 mole relative to the alkenyl groups such as vinyl and allyl groups in component (A), such that the amount of hydrogen atoms (hydrogenated silyl groups, i.e., Si-H groups) bonded to silicon atoms in component (B) is 0.1 to 2.5 moles, preferably 0.2 to 2 moles. If there is too little hydrogenated silyl group, the degree of cross-linking will be insufficient, resulting in the inability to obtain a cured product; if there is too much, foaming will occur during curing.

[0067] In the method for manufacturing the fluorinated organohydrosilane compound of component (B), the target compound can be separated after the reaction is completed. Furthermore, even mixtures containing unreacted substances or byproducts can be used later by removing the addition reaction catalyst, provided that the characteristics of the invention are not impaired. In any case, the hydrogenated silane (i.e., Si-H group) should be included in an amount of 0.1 to 2.5 mol, preferably 0.2 to 2 mol, relative to 1 mol of alkenyl groups such as vinyl and allyl groups in component (A).

[0068] (B) The ingredients may be used alone or in combination of two or more of the fluorinated organohydrosilane compounds.

[0069] [(C) Component] In the fluorinated polyether curable composition of the present invention, component (C) is a platinum group metal catalyst. This is a hydrogenated silanization reaction catalyst, which promotes the addition reaction of the alkenyl group in component (A) with the hydrogenated silyl group in component (B) and, as described later, any adhesion enhancer or adhesion accelerator. This hydrogenated silanization reaction catalyst is generally a compound of a noble metal; due to its high cost, platinum or platinum compounds, which are relatively easy to obtain, are mostly used.

[0070] Examples of platinum compounds include platinum chloride or its complexes with olefins such as ethylene, complexes with alcohols or vinyl siloxanes, and platinum supported on silicon dioxide, aluminum oxide, carbon, etc. Other platinum group metal catalysts besides platinum compounds include rhodium, ruthenium, iridium, and palladium compounds, such as RhCl(PPh 3) 3, RhCl(CO)(PPh 3) 2, Ru 3(CO) 12, IRCl(CO)(PPh 3) 2, and Pd(PPh 3) 4. Note that in the aforementioned formulas, Ph represents a phenyl group.

[0071] When these are used as catalysts, if they are solid catalysts, they can also be used in solid form. However, in order to obtain a more uniform cured product, it is better to dissolve the platinum chloride or chelate in a suitable solvent and then use it in combination with the perfluoropolyether compound of component (A).

[0072] (C) The amount of component used can be the amount of catalyst, for example, relative to the mass of component (A), preferably 0.1 to 1,000 ppm (platinum group metal atomic conversion), and more preferably 1 to 500 ppm. (C) Component can be used alone or in combination of two or more.

[0073] [Other ingredients] In the fluorinated polyether-based curable composition of the present invention, in order to improve its practicality, in addition to the components (A) to (C) mentioned above, various formulation agents such as adhesion enhancers (adhesion imparters), plasticizers, viscosity modifiers, flexibility imparters, inhibitors of hydrogenated silanization reaction catalysts, inorganic fillers, adhesion promoters, and silane coupling agents may be added as needed. The amount of these additives is arbitrary, provided that it does not impair the purpose of the present invention and the properties of the composition and the physical properties of the cured product.

[0074] The adhesion enhancer functions as an adhesion enhancer that enables the fluoropolyether-based curable composition of the present invention to exhibit self-adhesion by formulation. The adhesion enhancer is an organohydrosiloxane compound obtained by having one or more hydrogen atoms (Si-H groups) bonded to silicon atoms and one or more epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms through carbon atoms or carbon and oxygen atoms. Furthermore, since this adhesion enhancer has a molecular structure equivalent to fluorinated organohydrosiloxanes, although it is difficult to maintain self-adhesion for hydrofluoric acid or electrolytes for lithium-ion secondary batteries for a long time by using this adhesion enhancer, it is extremely effective in situations where initial self-adhesion is required, such as in the manufacture of articles having cured products obtained from the fluoropolyether-based curable composition of the present invention.

[0075] Of the aforementioned adhesion enhancers, those having one or more perfluoroalkyl groups or monovalent perfluoropolyether groups (perfluorooxyalkyl groups) per molecule are preferred. The aforementioned perfluoroalkyl groups or monovalent perfluoropolyether groups are bonded to silicon atoms through a divalent group containing at least one of oxygen, nitrogen, carbon, and silicon atoms, particularly through a divalent group containing nitrogen and carbon atoms, or through a divalent group containing nitrogen, carbon, and oxygen atoms. Examples of such perfluoroalkyl groups include those represented by CjF2j+1- (j is an integer from 1 to 10, preferably an integer from 3 to 7). Furthermore, examples of monovalent perfluoropolyether groups are those exemplified by Rf in formula (1) represented by component (B) above. Furthermore, as the divalent bonding group that connects the perfluoroalkyl or monovalent perfluoropolyether group to the silicon atom, a divalent organic group (preferably a hydrocarbon group) containing at least one of oxygen, nitrogen, and silicon atoms with 1 to 20 carbon atoms can be used.

[0076] The silicone skeleton of the organohydrogen polysiloxane compound used as an adhesion enhancer can be cyclic, linear, branched, or a mixture of two or more of these forms, preferably cyclic. The organohydrogen polysiloxane compound used as an adhesion enhancer can be represented by the following general formula.

[0077] (In the formula, R2 is a non-substituted or halogenated monovalent hydrocarbon group, L1 is a monovalent perfluoropolyether group bonded to silicon atoms through a divalent bonding group, and M...) 1 refers to the epoxy or trialkoxysilane group represented below, which is bonded to silicon atoms through carbon atoms or carbon and oxygen atoms. w2 is preferably an integer satisfying 0 ≤ w2 ≤ 50, and more preferably an integer satisfying 0 ≤ w2 ≤ 20; x2 is preferably an integer satisfying 1 ≤ x2 ≤ 50, and more preferably an integer satisfying 1 ≤ x2 ≤ 20; y2 is preferably an integer satisfying 0 ≤ y2 ≤ 50, and more preferably an integer satisfying 1 ≤ y2 ≤ 20; z2 is preferably an integer satisfying 1 ≤ z2 ≤ 50, and more preferably an integer satisfying 1 ≤ z2 ≤ 20. The repeating units represented in parentheses above may be randomly bonded.

[0078] The unsubstituted or halogenated monovalent hydrocarbon group of the above-mentioned R2 does not contain an aliphatic unsaturated bond, and is preferably composed of 1 to 10 carbon atoms, and even more preferably composed of 1 to 8 carbon atoms. Specifically, 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 phenethyl; or substituted monovalent hydrocarbon groups obtained by replacing part or all of the hydrogen atoms in such groups with halogen atoms such as fluorine, etc., with methyl being particularly preferred.

[0079] The L1 group described above is a monovalent perfluoropolyether group that is bonded to silicon atoms through a divalent bonding group, preferably represented by the following general formula. -Z-Rf 2 [In the formula, Rf 2 is a monovalent perfluoropolyether group, which is the same as Rf in the above general formula (1), and can be the same as the one exemplified by Rf. The Z-system may contain a divalent organic group (preferably a hydrocarbon group) selected from at least one of oxygen atom, nitrogen atom and silicon atom, having a carbon number of 1 to 20].

[0080] Examples of Z include -CH 2-*, -CH 2CH 2CH 2-*, -OCH 2-*, -CH 2OCH 2-*, and -(CH 2) 2OCH 2-*. -(CH 2) 3OCH 2-*, -CH 2-NH-CO-*, -(CH 2) 3-NH-CO-*, -(CH 2) 3-N(Me)-CO-*, -(CH 2) 3-N(Et)-CO-*, -(CH 2) 3-N(CH(Me) 2)-CO-*, -CH 2-N(Ph)-CO-*, -(CH 2) 3-O-CO-*, -CH 2OCH 2CH 2CH 2-Si(Me) 2-O-Si(Me) 2-(CH 2) 2-*、 -CO-N(Me)-Ph'-Si(Me) 2-(CH 2) 2-*, -CO-N(CH 2)-Ph'-Si(CH 2) 2-(CH 2) 2-Si(CH 2) 2-O-Si(CH 2) 2-(CH 2) 2-*, -CO-NH-Ph'-[Si(Me) 2-(CH 2) 2] 3-CH 2-*, -CO-N(Me)-Ph'-[Si(Me) 2-(CH 2) 2] 3-*, and the following groups, wherein -(CH 2) 3OCH 2-*, -(CH 2) 3-NH-CO-*, and the following groups are preferred. Also, Me-series groups represent methyl, Et-series groups represent ethyl, Ph-series groups represent phenyl, and Ph'-series groups represent phenylene. Furthermore, the bonding portion marked with an asterisk (*) indicates a bond with a monovalent perfluoropolyether group, while the bonding portion without an asterisk indicates a bond with a silicon atom in an organohydrogen polysiloxane.

[0081] The M 1 series mentioned above refers to epoxy or trialkoxysilyl groups that are bonded to silicon atoms through carbon atoms or carbon and oxygen atoms, specifically the following groups.

[0082] (In the formula, R 3 series represents a divalent hydrocarbon group with 1 to 10 carbon atoms (especially 1 to 5 carbon atoms) that can insert oxygen atoms (such as alkyl groups of methyl, ethyl, propyl, etc., alkyl groups of cyclohexyl, oxyethyl, oxypropyl, oxybutyl, etc., preferably -(CH 2) 3OCH 2-*' (the bonded part with *' indicates a bond with an epoxy group))).

[0083] -R 4-Si(OR 5) 3 (In the formula, R4 series represents divalent hydrocarbon groups with 1 to 10 carbons (especially 1 to 4 carbons) such as alkyl groups such as methyl, ethyl, propyl, etc., and R5 series independently represents monovalent hydrocarbon groups with 1 to 8 carbons (especially 1 to 4 carbons) such as alkyl groups such as methyl, ethyl, propyl, butyl, etc.)).

[0084] (In the formula, R6 represents a hydrogen atom or a methyl group, R7 represents a monovalent hydrocarbon group with 1 to 8 carbon atoms (especially alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc.), and l represents an integer from 2 to 10).

[0085] Organohydrogen polysiloxane compounds used as adhesion enhancers can be obtained by a partial addition reaction according to conventional methods, as follows: An organohydrogen polysiloxane having three or more hydrogen atoms bonded to silicon atoms (Si-H groups) per molecule is partially added to a compound containing aliphatic unsaturated groups such as vinyl and allyl groups, epoxy groups, and / or trialkoxysilyl groups, and further, depending on the desired compound containing aliphatic unsaturated groups and perfluoroalkyl or perfluorooxyalkyl groups. Furthermore, the number of aliphatic unsaturated groups must be less than the number of Si-H groups.

[0086] When manufacturing organohydropolysiloxane compounds used as adhesion enhancers, although the target substance can be separated after the reaction is complete, a mixture that only removes unreacted substances and addition reaction catalysts can also be used.

[0087] Organohydrogen polysiloxane compounds used as adhesion enhancers are specifically exemplified by those represented by the following structural formulas. Furthermore, such compounds may be used alone or in combination of two or more. Also, in the following formulas, Me represents methyl.

[0088] (In the formula, x2' = 2 or 3, b1' = integers from 2 to 20. The repeating units represented in parentheses may be random.)

[0089] (In the formula, x2' = 2 or 3, b1' = integers from 2 to 20. The repeating units represented in parentheses may be random.)

[0090] (In the formula, x2'' = 1 or 2, b1' = integers from 2 to 20. The repeating units represented in parentheses may be random.)

[0091] (In the formula, z2' = 2 or 3, b1' = integers from 2 to 20. The repeating units represented in parentheses may be random.)

[0092] (In the formula, y2' = 2 or 3, b1' = integers from 2 to 20. The repeating units represented in parentheses may be random.)

[0093] When preparing an adhesion enhancer, the amount of hydrogenated silyl (Si-H group) in the adhesion enhancer is preferably 0.005 to 0.5 mol relative to 1 mol of alkenyl group in component (A), more preferably 0.01 to 0.2 mol, and even more preferably 0.05 to 0.1 mol.

[0094] As a plasticizer, viscosity modifier, or flexibility enhancer, a polyfluorinated monoolefin compound represented by the following general formula (12) and / or a polyfluorinated compound represented by the following general formulas (13) and (14) may be used.

[0095] [In the formula, Z 1 may contain a divalent organic group (preferably a hydrocarbon group) with 1 to 20 carbon atoms selected from oxygen, nitrogen and silicon atoms, p2 is 0 or 1, and Rf 3 is a monovalent perfluoropolyether group represented by the following general formula.] (In the formula, f2 is an integer from 2 to 200, preferably an integer from 2 to 100, and h2 is an integer from 1 to 3, and is less than the molecular weight of Rf1 in formula (2) of component (A) used).

[0096] [In the formula, Y1 is independently represented by the formula: C k2F 2k2+1- (k2 is an integer from 1 to 3), c2 is an integer from 1 to 200, and is less than the molecular weight of Rf1 in formula (2) of the component (A) used].

[0097] (In the formula, Y2 is the same as Y1 above, d2 and e2 are integers from 1 to 200, and are less than the molecular weight of Rf1 in formula (2) of component (A) used. Each repeating unit represented in the above ( ) may be randomly bonded).

[0098] In the above general formula (12), the Z 1 system may contain a divalent organic group (preferably a hydrocarbon group) with 1 to 20 carbon atoms selected from oxygen atoms, nitrogen atoms and silicon atoms. In addition to being the same as Z (divalent bonding group) in the above L 1 structure, it may also be represented as shown below (in the formulas shown below and for Z, the bonding part with * indicates a bond with Rf 3, and the bonding part without * indicates a bond with a carbon atom. Also, Me system represents methyl).

[0099] As a specific example of the polyfluorinated monoolefin compound represented by the above general formula (12), the following can be cited. Also, the following f2 is one that satisfies the above requirements.

[0100]

[0101] As specific examples of polyfluorinated compounds represented by the above general formulas (13) and (14), the following can be cited. Also, the following c2, d2, e2 and the sum of d2 and e2 satisfy the above requirements.

[0102] The viscosity (23°C) of the polyfluorinated monoolefin compound of formula (12) and the polyfluorinated compounds of formulas (13) and (14) is preferably in the range of 2,000 to 50,000 mPA·s. Furthermore, when preparing the polyfluorinated monoolefin compound of formula (12) and the polyfluorinated compounds of formulas (13) and (14), the amount prepared is preferably 1 to 300 parts by mass relative to 100 parts by mass of component (A), and even more preferably 50 to 250 parts by mass.

[0103] Furthermore, as inhibitors for the hydrogenation silanization reaction catalyst, examples include alkynyl 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-pentyn-3-ol, and phenylbutynol; reactants of chlorosilanes with the aforementioned monovalent fluorinated substituents and alkynyl alcohols; 3-methyl-3-penten-1-yne; 3,5-dimethyl-3-hexen-1-yne; triallyl isocyanurate; polyvinylsiloxanes; and organophosphorus compounds. By adding these inhibitors, the curing reactivity and storage stability can be appropriately maintained. The dosage of this inhibitor is arbitrary, within the range that imparts the desired curing reactivity and storage stability.

[0104] As an inorganic filler, various silica powders can be added, such as fumed silica (gas-phase silica or dry silica), settled silica (wet silica), spherical silica (molten silica), sol-gel silica, silica aerogel, etc., or silica powders obtained by hydrophobicating the untreated surface of the silica powder with various organochlorosilanes, organodiazines, cyclic organopolysilazanes, etc. Reinforcing or semi-reinforcing fillers for surface-treated silica powder, quartz powder, fused silica powder, diatomaceous earth, calcium carbonate, etc.; inorganic pigments such as titanium dioxide, iron oxide, carbon black, cobalt aluminate, etc.; heat-resistant enhancers for titanium dioxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate, etc.; thermal conductivity imparting agents for alumina, boron nitride, silicon carbide, metal powders, etc.; and electrical conductivity imparting agents for carbon black, silver powder, conductive zinc oxide, etc.

[0105] When the aforementioned adhesion enhancer is included, the adhesion accelerator improves the adhesion-imparting ability of the adhesion enhancer and promotes the self-adhesion of the cured product obtained by curing the fluorinated polyether curable composition of the present invention. Carboxylic anhydrides are particularly suitable for use.

[0106] Examples of carboxylic anhydrides include those that are solid at 23°C. Specifically, the following compounds can be cited as examples. In the following formulas, Me represents methyl groups.

[0107] Furthermore, the carboxylic anhydride can be a cyclic organopolysiloxane (i.e., a fluorinated organopolysiloxane-modified carboxylic anhydride compound) having a hydrogen atom directly bonded to a silicon atom, a perfluoroalkyl group or a perfluorooxyalkyl group, and a cyclic carboxylic anhydride residue in one molecule, wherein the aforementioned perfluoroalkyl group or perfluorooxyalkyl group is bonded to the silicon atom through a divalent hydrocarbon group that may contain at least one of oxygen, nitrogen, and silicon atoms, and the aforementioned cyclic carboxylic anhydride residue is bonded to the silicon atom through a divalent hydrocarbon group. Examples of such compounds include those represented by the following general formula (15). While it is difficult to maintain self-adhesion to electrolytes for hydrofluoric acid or lithium-ion secondary batteries for a long time by using this compound, since the fluorinated organosiloxane modified carboxylic anhydride compound has a molecular structure equivalent to that of fluorinated organohydrosiloxane, it is extremely effective in situations where initial self-adhesion is required, such as in the process of manufacturing articles having cured articles obtained from the fluorinated polyether curable composition of the present invention. (In the formula, L2 is a monovalent perfluoropolyether group bonded to silicon atoms through a divalent hydrocarbon group, J is a cyclic carboxylic anhydride residue bonded to silicon atoms through a divalent hydrocarbon group, R8 is a monovalent hydrocarbon group that is unsubstituted or halogenated, t2 is an integer from 1 to 6, u2 is an integer from 1 to 4, v2 is an integer from 1 to 4, t2+u2+v2 is an integer from 4 to 10, and the repeating units represented in the parentheses above can be randomly bonded).

[0108] In the above formula (15), L2 is a monovalent perfluoropolyether group that bonds to silicon atoms through a divalent hydrocarbon group. Examples of groups similar to L1 can be cited. These groups are introduced from the viewpoints of compatibility, dispersibility and uniformity after hardening of component (A).

[0109] Furthermore, in the above formula (15), R8 is a non-substituted or halogenated monovalent hydrocarbon group, and the same group as R2 mentioned above can be cited, with methyl and ethyl being preferred.

[0110] Furthermore, in the above formula (15), J is a cyclic carboxylic anhydride residue that is bonded to silicon atoms through a divalent hydrocarbon group, specifically the group represented by the following general formula.

[0111] In the above formula, R is a divalent hydrocarbon group with 2 to 15 carbon atoms, specifically including ethyl, propyl, and butyl groups, among which propyl is preferred.

[0112] Furthermore, in the above formula (15), t2 is an integer from 1 to 6, preferably an integer from 2 to 5; u2 is an integer from 1 to 4, preferably an integer from 1 to 3; v2 is an integer from 1 to 4, preferably an integer from 1 to 3; and t2+u2+v2 is an integer from 4 to 10, preferably an integer from 4 to 8. However, the arrangement order of ((H)(R 8)SiO) units, ((L 2)(R 8)SiO) units, and ((J)(R 8)SiO) units is random.

[0113] Examples of cyclic organopolysiloxanes represented by the above general formula (15) include the following compounds. In the following formulas, Me represents methyl. (In the formula, t2' = 2 or 3, b2' = an integer from 2 to 20) (In the formula, v2' = 2 or 3, b2' = an integer from 2 to 20)

[0114] The adhesion promoters used may be a single type or two or more types used in combination. In this case, the carboxylic anhydride that is solid at 23°C may be used in combination with the cyclic organopolysiloxane (fluorinated organopolysiloxane modified carboxylic anhydride compound).

[0115] When preparing the adhesion accelerator, the amount prepared is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of component (A), and more preferably 0.05 to 1 part by mass. Furthermore, the amount of hydrogenated silyl (Si-H group) in the adhesion accelerator is preferably 0.005 to 0.5 mol (most preferably 0.05 to 0.1 mol) relative to 1 mol of alkenyl group in component (A). The total amount of hydrogenated silyl groups contained in the composition (especially the total amount of hydrogenated silyl groups in component (B), adhesion enhancer and adhesion accelerator) is preferably 0.1 to 2.5 mol (most preferably 0.2 to 2 mol) relative to 1 mol of alkenyl group in component (A).

[0116] [Manufacturing method of fluoropolyether-based curable components] The method for manufacturing the fluoropolyether-based curable composition of the present invention is not particularly limited, and can be manufactured by mixing the above-mentioned components. Specifically, the fluoropolyether-based curable composition of the present invention is manufactured by uniformly mixing the above-mentioned components (A) to (C) with other arbitrary components using a mixing device such as a planetary mixer, Ross mixer, or Hobart mixer, and by using a kneading device such as a kneader or a three-axis roller as needed. Alternatively, it can be formulated into a two-component mixture and mixed before use.

[0117] Depending on the type of catalyst in component (C), the manufactured fluorinated polyether curable composition can also be cured at room temperature, but heating is preferable to promote curing. In particular, to achieve good adhesion to various substrates, it is preferable to cure it at 60°C or above (preferably 100~200°C) for several minutes to several hours.

[0118] Furthermore, when using the fluorinated polyether-based curable composition of the present invention, the composition can be dissolved in a suitable fluorinated solvent (e.g., 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, etc.) at the desired concentration depending on its application and purpose. The use of a solvent is particularly preferred for thin film coating applications.

[0119] The fluorinated polyether curable composition of the present invention is preferably used as electrical and electronic parts for automobiles, chemical plants, semiconductor manufacturing lines, analytical and physical chemical machinery, living environments, communication machines, communication equipment, aircraft, railway vehicles, portable machines, power storage devices, robots, or lithium-ion batteries. In particular, it is preferable to use the cured form of the fluorinated polyether curable composition of the present invention as an electrical or electronic component, such as a sealing pad, a gasket, a protective sealant, or a coating layer. [Example]

[0120] The present invention will be described in more detail below with reference to synthetic examples, embodiments, and comparative examples, but the present invention is not limited to the embodiments described below. Also, in the examples below, Me represents methyl groups, and parts represent parts by mass. Furthermore, AK-225 (manufactured by Asahi Glass Co., Ltd.), a fluorinated solvent, was used as the developing solvent to determine the number average molecular weight of polystyrene in gel permeation chromatography (GPC) analysis, which was then used as the number average molecular weight. Viscosity (23°C) is a value measured according to the method of a rotational viscometer for viscosity testing as specified in JIS K6249.

[0121] Synthesis of fluorinated organohydrosilane compounds [Synthesis example 1] In a 1L flask, an organohydrosilane compound represented by the following formula (16) is added (hydrosilane content 0.616mol / 100g). 150g of the compound represented by the following formula (17) (vinyl content 0.0681mol / 100g) 339g of 1,3-bis(trifluoromethylbenzene) and 91g of nitrogen substitution were carried out. After heating 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), and stirred for 1 hour with 9.10 g of activated carbon (trade name: Shirogane AS, manufactured by Osaka Gas Chemicals) and then filtered. Activated carbon (9.10 g) was added to the resulting solution, and the mixture was stirred for 1 hour and then filtered. By using separation liquid chromatography, the main component was extracted from the obtained solution and then concentrated under reduced pressure to obtain 376g of the compound represented by the following formula (18) (hydrogenated silane content 0.143mol / 100g). The 1H-NMR spectrum of the obtained product was confirmed to contain 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), thus confirming the formation of the compound represented by the above formula (18).

[0122] [Synthesis example 2] Except for replacing the compound represented by formula (17) with 1,012 g of the compound represented by formula (19) (vinyl content 0.0228 mol / 100g), The same procedure as in Synthesis Example 1 was performed to obtain the compound represented by the following formula (20) (hydrogenated silane content: 0.0682 mol / 100 g). The 1H-NMR spectrum of the obtained product was confirmed to contain 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), and it was confirmed to be the formation of the compound represented by the above formula (20).

[0123] [Synthesis example 3] In addition to replacing the compound represented by formula (16) with 85g of the compound represented by formula (21) (hydrogenated silane content 1.09mol / 100g), The same procedure as in Synthesis Example 1 was performed to obtain 323 g of the compound represented by the following formula (22) (hydrogenated silane content: 0.247 mol / 100 g). The following signals were confirmed in the 1H-NMR spectrum of the obtained product: δ 7.85~6.55 (m, 4H), 4.29~3.51 (m, 5H), 3.15 (s, 3H), 1.23~-0.91 (m, 62H), thus confirming the formation of the compound represented by the above formula (22).

[0124] [Synthesis Example 4] Except for replacing the compound represented by formula (17) with 264g of the compound represented by formula (23) (vinyl content 0.0873mol / 100g), (The average of m+n is 12, and the ratio of m to n is 0.98:1) All operations were performed in the same manner as in Synthesis Example 1, and 317 g of the compound represented by the following formula (24) (hydrogenated silane content: 0.169 mol / 100 g) was obtained. (The average of m+n is 12, and the ratio of m to n is 0.98:1) The following signals were confirmed in the 1H-NMR spectrum of the obtained product: 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), 1.18~-0.90 (m, 44H), thus confirming the formation of the compound represented by the above formula (24).

[0125] <Preparation of fluorinated polyether-based curable components and confirmation of the compatibility between component (B) and component (A) (base oil)> [Example 1] To prepare a curable composition, 0.1 parts of a toluene solution (platinum concentration 0.5 wt%) of platinum-divinyltetramethyldisiloxane complex (C1), 0.07 parts of the compound represented by formula (26) below, and 9.74 parts of the compound represented by formula (18) below obtained in Synthesis Example 1 (hydrogenated silyl content 0.143 mol / 100g) were added to 100 parts of polymer (A1) represented by formula (25) below (number average molecular weight 15,550, viscosity 10,900 mPA·s, vinyl content 0.012 mol / 100g) and mixed to obtain a transparent oil. This demonstrates high compatibility between component (B1) and component (A1). (In the formula, m and n are integers greater than or equal to 1, and the average value of m+n is 90).

[0126] [Example 2] In Example 1, except that 100 parts of the polymer represented by formula (27) below (A2) (average molecular weight 15,630, viscosity 11,000 mPA·s, vinyl content 0.012 mol / 100g) were used to replace the polymer represented by formula (25) above in Example 1, the curing composition was prepared in the same manner as in Example 1 to obtain a transparent oil. This demonstrates that the compatibility between component (B1) and component (A2) is high. (In the formula, m and n are integers greater than or equal to 1, and the average value of m+n is 90).

[0127] [Example 3] In Example 1, except for 100 parts of the polymer represented by formula (28) below (A3) (average molecular weight 3,350, viscosity 60 mPA·s, vinyl content 0.031 mol / 100g) and 25.16 parts of the compound represented by formula (18) above (B1) to replace the polymer represented by formula (25) above (A1), the curing composition was prepared in the same manner as in Example 1, thereby obtaining a transparent oil. This demonstrates that the compatibility between component (B1) and component (A3) is high. (m:n = 0.98:1, average of m+n = 34)

[0128] [Example 4] In Example 1, except that 20.42 parts of the compound represented by formula (20) obtained in Synthesis Example 2 (Hydrogenated silane content: 0.0682 mol / 100 g) were used to replace the compound represented by formula (18) above in Example 1, the curing composition was prepared in the same manner as in Example 1 to obtain a transparent oil. This demonstrates that the compatibility between component (B2) and component (A1) is high.

[0129] [Example 5] In Example 1, except that 5.73 parts of the compound represented by formula (22) obtained in Synthesis Example 3 (Hydrogenated silane content: 0.247 mol / 100 g) were used to replace the compound represented by formula (18) above in (B1), the curing composition was prepared in the same manner as in Example 1, thereby obtaining a transparent oil. This demonstrates that the compatibility between component (B3) and component (A1) is high.

[0130] [Example 6] In Example 1, except that 8.24 parts of the compound represented by formula (24) obtained in Synthesis Example 4 (Hydrogenated silane content: 0.169 mol / 100 g) were used to replace the compound represented by formula (18) in Example 1, the curing composition was prepared in the same manner as in Example 1 to obtain a transparent oil. This demonstrates that the compatibility between component (B4) and component (A1) is high. (m:n=0.98:1, average of m+n=12).

[0131] [Example 7] In Example 1, except for the use of 9.61 parts of a mixture of compounds represented by formula (18) above (B5, which is obtained by directly concentrating the solution obtained in Synthesis Example 1 under reduced pressure without using separation liquid chromatography to extract the main component, and the other components were obtained in the same manner), and compounds represented by formulas (29), (30), (31) and (32) below (mass ratio: (18) / (29) / (30) / (31) / (32)=80:9:6:1:4, amount of hydrogenated silane: 0.145mol / 100g), to replace the compound represented by formula (18) above (B1), the other components were prepared in the same manner as in Example 1 to obtain a transparent oil. This demonstrates that the compatibility between component (B5) and component (A1) is high.

[0132] [Comparative Example 1] In Example 1, except for replacing the compound represented by formula (18) of formula (B1) with 2.26 parts of compound (B6) represented by formula (32) above (0.616 mol / 100 g of hydrogenated silane), the curing composition was prepared in the same manner as in Example 1, thereby obtaining a cloudy oil. This shows that the compatibility between component (B6) and component (A1) is low.

[0133] [Comparative Example 2] In Example 1, except that 3.52 parts of the compound represented by formula (33) below (Patent Document 5: Japanese Patent Application Publication No. 2002-012769, Example 1, amount of hydrogenated silane: 0.408 mol / 100 g) were used to replace the compound represented by formula (18) above (B1), the curing composition was prepared in the same manner as in Example 1, thereby obtaining a slightly turbid oil. This shows that the compatibility between component (B7) and component (A1) is low.

[0134] [Comparative Example 3] In Example 1, except that 3.54 parts of compound (B8) represented by formula (34) below (0.394 mol / 100 g of hydrogenated silane) were used to replace compound (B1) represented by formula (18) above, the curing composition was prepared in the same manner as in Example 1 to obtain a transparent oil. This demonstrates that component (B8) and component (A1) have high compatibility.

[0135] <Confirmation of the presence or absence of oily components (uncured portions) on the surface of fluoropolyether-based cured materials, and assessment of the release properties of the cured materials> 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 sheet made of TEFLON (registered trademark, hereinafter the same). After being clamped by other TEFLON sheets, they were pressure-cured at 150°C for 10 minutes. The demolding properties of the cured fluoropolyether composition after pressure curing and removal of the 2mm thick stainless steel mold, as well as the residual oily components on the surface of the cured composition, were evaluated according to the following evaluation criteria. The results, along with the appearance of the cured fluoropolyether composition, are shown in Table 1. [Evaluation Benchmarks] ○: It can be easily peeled off from the TEFLON sheet without damaging the hardened material, and no oily residue was found on the surface of the peeled hardened material. ×: It is difficult to peel the TEFLON sheet without damaging the hardened material, and an oily residue is found on the surface of the peeled hardened material.

[0136] [Table 1] Fluoropolyether Appearance of hardened components Presence or absence of oily components; release properties Example 1 transparent ○ Example 2 transparent ○ Example 3 transparent ○ Example 4 transparent ○ Example 5 transparent ○ Example 6 transparent ○ Example 7 transparent ○ Comparative Example 1 White discharge × Comparative Example 2 Slightly cloudy × Comparative Example 3 transparent ○

[0137] No uncured oily components were found dispersed on the surface of the fluoropolyether-based cured compositions obtained from Examples 1-7 and Comparative Example 3. This is because component (B) in the fluoropolyether-based cured compositions of Examples 1-7 and Comparative Example 3 exhibits high compatibility with component (A), resulting in almost all of component (B) reacting with component (A). Furthermore, it was confirmed that the cured composition could be easily peeled off from the TEFLON sheet after pressure curing, indicating no problem with demolding. On the other hand, uncured oily components were found dispersed on the surface of the fluoropolyether-based cured compositions obtained from Comparative Examples 1 and 2. This is believed to be because components (B6) and (B7) have poor compatibility with component (A), resulting in insufficient reaction with component (A) during heat curing, thus leaving unreacted components as oily residues on the surface of the fluoropolyether-based cured compositions. Furthermore, the hardened material is cured and adhered to the TEFLON sheet by pressure curing. When it is peeled off from the TEFLON sheet, the hardened material breaks or breaks, resulting in low demolding performance.

[0138] The fluorinated polyether-based cured materials obtained above were post-cured at 200°C for 4 hours, and their heat resistance, chemical resistance, solvent resistance, and electrolyte resistance were evaluated. The results are shown in Tables 2-5.

[0139] <Heat resistance> The physical properties of the fluoropolyether-based cured compositions obtained from Examples 1-7 and Comparative Examples 1-3 were evaluated according to JIS K 6249. Next, the fluoropolyether-based cured compositions obtained from Examples 1-7 and Comparative Examples 1-3 were placed in an oven at 150°C for 7 days, and the physical properties of the cured compositions were evaluated according to JIS K 6249. The change in hardness, the rate of change in tensile strength (%), and the rate of change in elongation at cut (%) were calculated using the following formulas. The results are shown in Table 2.

[0140] Hardness change = (hardness of the hardened material after 7 days at 150℃) - (initial hardness of the hardened material) Tensile strength change rate (%) = ((tensile strength of the hardened material after 7 days at 150℃) - (initial tensile strength of the hardened material)) / (initial tensile strength of the hardened material) × 100 Elongation at cut (%) = ((Elongation at cut of hardened material after 7 days at 150℃) - (Elongation at cut of hardened material in the initial stage)) / (Elongation at cut of hardened material in the initial stage) × 100

[0141] [Table 2]

[0142] <Drug Resistance> Fluoropolyether-based cured compositions obtained from Examples 1-7 and Comparative Examples 1-3 were immersed in concentrated hydrochloric acid, concentrated sulfuric acid, concentrated hydrofluoric acid, trifluoroacetic acid, and 40% KOH (potassium hydroxide) aqueous solution at 20°C for 3 days. The hardness before immersion was used as a reference to measure the change in hardness. The method for calculating the change in hardness was the same mathematical formula used in the heat resistance test. The results are shown in Table 3.

[0143] [Table 3]

[0144] The results in Table 3 confirm that the cured products obtained from the fluorinated polyether curing compositions of Examples 1-7 and Comparative Examples 1 and 2 exhibit excellent durability for all of the aforementioned pharmaceuticals. On the other hand, it can be confirmed that the cured product obtained from the fluorinated polyether curing composition of Comparative Example 3 has poor durability for concentrated hydrofluoric acid and trifluoroacetic acid.

[0145] Solvent resistance Fluoropolyether-based cured compositions obtained from Examples 1-7 and Comparative Examples 1-3 were used to conduct immersion tests (immersion time: 70 hours) with various organic solvents listed in Table 4 according to JIS K 6258. The volume change rate (%) before and after immersion was measured and the solvent swelling resistance was evaluated. The results are shown in Table 4.

[0146] [Table 4]

[0147] As can be confirmed from the results in Table 4, the cured products obtained from the fluorinated polyether curing compositions of Examples 1 to 7, like the cured products obtained from the curing fluorinated polyether curing compositions of Comparative Examples 1 to 3, exhibit excellent durability against all of the above solvents.

[0148] Electrolyte Resistance Fluoropolyether-based cured products obtained from the fluorinated polyether-based 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. Based on the changes in hardness, adhesion, and appearance of the cured products before and after immersion, the degree of degradation of the cured products was evaluated according to the following evaluation criteria.

[0149] [Evaluation Benchmarks] [hardness] ○: Almost no change in hardness was observed before and after immersion in the electrolyte for lithium-ion batteries. ×: Because the electrolyte used for immersing lithium-ion batteries was used, a significant decrease in hardness was observed. [Adhesive] ○: There was no change in adhesion on the surface of the hardened material due to immersion in lithium-ion battery electrolyte. ×: The surface of the hardened material becomes sticky because it is soaked in the electrolyte used in lithium-ion batteries. [Appearance] ○: Almost no change in appearance was observed before and after immersion in the electrolyte for lithium-ion batteries. ×: Because the electrolyte used for immersion in lithium-ion batteries was found to cause swelling, deformation, and decomposition of the hardened material.

[0150] [Table 5]

[0151] The cured products obtained from the fluorinated polyether-based curable compositions of Examples 1-7 and Comparative Examples 1 and 2 showed almost no change in hardness, surface adhesion, or appearance before and after immersion in lithium-ion battery electrolyte. This indicates that the aforementioned compositions and cured products are suitable for lithium-ion battery applications. On the other hand, it was confirmed that the cured product obtained from the fluorinated polyether-based curable composition of Comparative Example 3 experienced swelling and surface decomposition after immersion in lithium-ion battery electrolyte. Furthermore, when the two ends of this cured product were stretched, it easily broke into filaments.

[0152] Based on the above results, it can be seen that the cured products obtained from the fluorinated polyether curable compositions of Examples 1 to 7 have both durability and release properties for hydrofluoric acid or lithium-ion battery electrolytes, thus demonstrating the effects of the present invention.

Claims

1. A fluoropolyether-based curable composition comprising the following components: (A) 100 parts by mass of a perfluoropolyether compound having two or more alkenyl groups in one molecule; (B) a fluorinated organohydrosilane compound having two or more hydrogenated silyl groups as represented by the following general formula (1): the amount of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 2.5 mol relative to 1 mol of alkenyl groups in component (A); and (C) a platinum group metal catalyst: 0.1 to 2,000 ppm relative to the mass of component (A) in platinum group metal atom conversions. (In the formula, Rf is a monovalent perfluoropolyether group, A is a divalent organic group with 1 to 20 carbon atoms that may contain at least one of oxygen, nitrogen and silicon atoms, R is a monovalent hydrocarbon group with 1 to 6 carbon atoms, x is an integer from 1 to 3, B is a monovalent organic group that has one or more diorganohydrosilyl groups and forms a silyl group structure with the attached silicon atom, if x is 1, B has two or more diorganohydrosilyl groups, and y is 1 or 2).

2. If the fluorinated polyether in claim 1 is a curable component, wherein, (A) The component is a perfluoropolyether compound represented by the following general formula (2), [where A1 is an organic group with a carbon number of 1 to 20 that may contain at least one of oxygen, nitrogen and silicon atoms, B1 is a carbon atom or a silicon atom, X is a hydrogen atom, a methyl group or an alkenyl group with a carbon number of 2 to 8, but at least two of X are alkenyl groups with a carbon number of 2 to 8, and if X is a hydrogen atom, the bonded B1 is a carbon atom, and Rf1 is a divalent perfluoropolyether group].

3. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, In component (B), Rf in the above general formula (1) is a base represented by the following general formula (5), (where D is a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, a, b, c and d are each independent integers from 0 to 100, and 2≦a+b+c+d≦100, e is an integer from 1 to 3, and each repeating unit represented in the above ( ) may be randomly bonded, and each of these units may be linear or branched).

4. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, In component (B), the A group in the above general formula (1) is selected from the following groups: alkyl groups having 1 to 12 carbon atoms, alkyl groups containing aryl groups having 6 to 8 carbon atoms, divalent groups formed by alkyl groups bonded to each other through two organosilicon groups, divalent groups formed by alkyl groups and aryl groups bonded through two organosilicon groups, and such groups further having at least one divalent group selected from ether-bonded oxygen atoms, secondary amino groups, tertiary amino groups and amide bonds.

5. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, In component (B), A in the above general formula (1) is any one of the bases represented by the following general formulas (6) to (9), (where X0 is a hydrogen atom, methyl or ethyl, X1 is independently a hydrogen atom, fluorine atom, methyl, ethyl or trifluoromethyl, X2 is a hydrogen atom, methyl, ethyl, isopropyl or phenyl, R' is independently methyl or ethyl, f is an integer from 1 to 6, t is 0 or 1, and the bonding part with * indicates a bond with the Si atom in the above general formula (1), and the unmarked bonding part indicates a bond with Rf).

6. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, In component (B), R in the above general formula (1) is any one of methyl, ethyl, isopropyl, tributyl, or phenyl.

7. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, In component (B), there are two or more silyl groups in the molecular chain between Rf in the above general formula (1) and the diorganohydrosilyl group in B.

8. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, In component (B), B in the above general formula (1) is a base represented by the following general formula (10), [where 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, E is a hydrogen atom or a base represented by the following formula, (where R is the same as above, p' is an integer from 1 to 6, q' is an integer from 0 to 6) (but, when E is a hydrogen atom, r is 1), and each repeating unit represented in the parentheses of p, q or p', q' above may be randomly bonded].

9. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, (B) The components are selected from fluorinated organohydrosilane compounds represented by the following formula (where b' is an integer from 2 to 100, c''' and d'' are integers from 1 to 99, and c'''+d''=2 to 100, Me is methyl, Et is ethyl, Ph is phenyl, and the repeating units represented in the parentheses of c''' and d'' can be randomly bonded).

10. If the fluorinated polyether in claim 1 or 2 is a curable component, it is for use in lithium-ion batteries.

11. If the fluorinated polyether in claim 1 or 2 is a curable component, wherein, The base oil system consists of only component (A).

12. A cured product obtained from any one of the fluoropolyether-based curable compositions in claims 1 to 11.

13. An electrical or electronic component having a hardened material as claimed in claim 12.

14. Electrical and electronic components as described in claim 13, wherein, The hardened material is a sealing gasket, sealing pad, protective sealant, or coating layer.

15. Electrical and electronic components as requested in items 13 or 14, which are for use in automobiles, chemical plants, semiconductor manufacturing lines, analytical and physical chemical machinery, living environments, communication equipment, communication devices, aircraft, railway vehicles, portable machines, power storage devices, robots, or lithium-ion batteries.

16. Electrical and electronic components as described in claim 15, which are for use in lithium-ion batteries.

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