Curable perfluoropolyether gel composition, perfluoropolyether gel cured product, and electronic component sealed by cured product

Abstract

The present invention is a curable perfluoropolyether gel composition containing the following components (A) to (D): (A) 10-90 parts by mass of a linear perfluoropolyether compound having two or more alkenyl groups in one molecule; (B) 10-90 parts by mass of a perfluoropolyether compound that does not have an alkenyl group in the molecule; (C) a curing effective dose of an organohydrogenpolysiloxane having two or more hydrosilyl groups in one molecule; and (D) a hydrosilylation reaction catalyst in a catalytic amount. As a result, provided is a curable perfluoropolyether gel composition which has excellent chemical resistance, low-temperature characteristics, and the like, and which is capable of suppressing leakage of a plasticizer during a heat resistance test.

Description

Technical Field

[0001] This invention relates to a curable perfluoropolyether gel composition, a cured perfluoropolyether gel formed by curing the composition, and electronic components sealed by the cured gel. The cured perfluoropolyether gel composition exhibits excellent heat resistance, chemical resistance, low-temperature properties, and sealing properties after curing. It can suppress the leakage of plasticizers during heat resistance tests, thereby improving reliability. Background Technology

[0002] A fluorinated gel composition is known, which uses a divalent perfluoropolyether group having two alkenes in one molecule as the main agent, and contains an organohydrogen polysiloxane having hydrogen atoms bonded to silicon atoms, and a platinum group metal catalyst. It has been reported that a fluorinated polyether gel cured product with excellent chemical resistance, solvent resistance and heat resistance is provided by curing (Patent Document 1, Patent Document 2).

[0003] In the aforementioned addition-curing fluoropolyether gel compositions, a fully fluorinated perfluoropolyether compound is incorporated as a plasticizer to control penetration. Generally, the hydrocarbon groups in this plasticizer are fully fluorinated in the polymer. However, when targeting fluoropolyether gels with particularly high penetration, increasing the proportion of this plasticizer can lead to leakage problems during heat resistance tests. This is believed to be because various fluoropolymers contain non-fluorinated groups such as alkenyl and SiH groups for hydrosilylation, which reduces their compatibility with the fully fluorinated perfluoropolyether plasticizer.

[0004] Existing technical documents Patent documents

[0005] Patent Document 1: Japanese Patent No. 4098699 Patent Document 2: Japanese Patent No. 6020327 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] The present invention was made in view of the above circumstances, and its object is to provide a curable perfluoropolyether gel composition, a cured perfluoropolyether gel formed by curing the composition, and electronic components sealed by the cured product. The curable perfluoropolyether gel composition has excellent heat resistance, chemical resistance, low temperature characteristics, and sealing properties after curing. In particular, by using a perfluoropolyether compound that is not fully fluorinated and has a portion of hydrocarbon groups but no alkenyl groups as a plasticizer, the leakage of plasticizer can be suppressed during heat resistance tests, thereby improving reliability.

[0008] Methods for solving problems

[0009] To address the aforementioned problems, this invention provides a curable perfluoropolyether gel composition, a cured product thereof, and electronic components sealed by the cured product, wherein the curable perfluoropolyether gel composition contains the following components (A) to (D): (A) 10 to 90 parts by mass of an ingredient having at least two alkenyl groups in one molecule and containing -C in the main chain. a F 2a Perfluoropolyether compounds with repeating O- units and perfluoropolyether structures, wherein a is an integer from 1 to 6; (B) 10 to 90 parts by mass of a perfluoropolyether compound that does not have an alkenyl group in its molecule, selected from at least one of the compounds represented by the following general formulas (1) and (2), wherein the total of components (A) and (B) is 100 parts by mass. Rf 1 -C(=O)-NR1R2(1) R2R1N-C(=O)-Rf 2 -C(=O)-NR1R2(2) In equation (1), Rf 1 It is a monovalent perfluoropolyether group, in formula (2), Rf 2 It is a divalent perfluoropolyether group, where R1 in formula (1) and formula (2) is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group, and R2 is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group. (C) A curing effective dose of an organohydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule; (D) Catalyst amount for hydrogenation silylation reaction.

[0010] If it is a curable perfluoropolyether gel composition containing components (A) to (D) of the present invention, it will become a curable perfluoropolyether gel composition (fluorine-containing curable gel composition), which has excellent heat resistance, chemical resistance, low temperature characteristics, and adhesion after curing. In particular, it can suppress the leakage of plasticizer during heat resistance tests, and can be used to improve reliability.

[0011] Additionally, a curable perfluoropolyether gel composition is provided, wherein component (A) is a perfluoropolyether compound represented by the following general formula (3): [Chemical Formula 1]

[0012] In the formula, X is -CH2-, -CH2O-, -CH2OCH2-, or -Y-NR 1-CO-, where Y is -CH2- or a group represented by the following structural formula (Z), R 1 X' is a hydrogen atom, methyl, phenyl, or allyl group; X' is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR. 2 -Y'-, where Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 It can be a hydrogen atom, methyl, phenyl, or allyl; p is independently 0 or 1; r is an integer from 2 to 6; m and n are independent integers, m≥1, n≥1, 2≤m+n≤200; [Chemical Formula 2]

[0013] [Chemical Formula 3] .

[0014] If it is a curable perfluoropolyether gel composition containing this component (A), it will become a curable perfluoropolyether gel composition with excellent heat resistance, chemical resistance, low temperature characteristics, and adhesion after curing. In particular, it can suppress the leakage of plasticizer during heat resistance tests, thus improving reliability.

[0015] Additionally, a curable perfluoropolyether gel composition is provided, wherein the Rf in general formula (1) of component (B) is... 1 For F-[CF(CF3)CF2O] w -CF(CF3)- represents a perfluoropolyether compound, where w represents an integer from 1 to 200; or Rf in the general formula (2) of component (B) 2 For -CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)- represents a perfluoropolyether compound, where r is an integer from 2 to 6; m and n are independent integers, m≥1, n≥1, 2≤m+n≤200.

[0016] If it is a curable perfluoropolyether gel composition containing this component (B), it will become a gel composition and its cured product, which can prevent the leakage of plasticizers, in particular, while maintaining physical properties such as chemical resistance.

[0017] Additionally, a curable perfluoropolyether gel composition is provided, which, depending on demand, further comprises, as component (E), a polyfluoromonoolefinic compound represented by the following general formula (4) as an arbitrary component: Rf 3 -(X 2 ) p＇ -CH=CH2(4) In the formula, X 2 -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR 2 -Y 2 -, where Y 2 It is -CH2- or composed of the following structural formula (Z 2 () represents a group, [Chemical Formula 4]

[0018] The structural formula (Z) 2 The group represented by ) is a dimethylphenylmethylenesilyl group represented by the ortho, meta, or para position; R 2 For hydrogen atoms, methyl, phenyl, or allyl groups; p' is 0 or 1; Rf 3 For the general formula F-[CF(CF3)CF2O] w＇ -CF(CF3)- represents the perfluoropolyether structure, where w' is represented by an integer from 1 to 300.

[0019] If the curable perfluoropolyether gel composition contains this component (E), it will become a gel curing material that, while maintaining physical properties such as chemical resistance, moderately reduces the crosslinking density and prevents plasticizer leakage during heat resistance testing.

[0020] Additionally, a curable perfluoropolyether gel composition is provided, wherein the (D) component is a catalyst activated by heat or light.

[0021] If it is a curable perfluoropolyether gel composition containing this component (D), it will be suitable for applications where heating is not possible during curing, for example.

[0022] In addition, the present invention provides a perfluoropolyether gel cured product, which is obtained by curing the above-mentioned curable perfluoropolyether gel composition.

[0023] If it is a perfluoropolyether gel cured material, it has excellent heat resistance, chemical resistance, low temperature characteristics, and adhesion. It can prevent plasticizer leakage at high temperatures and is useful for bonding, sealing materials, and coating materials for electronic components.

[0024] In addition, the present invention provides electronic components sealed by the cured product of the curable perfluoropolyether gel composition (i.e., perfluoropolyether gel), particularly pressure sensors, hydraulic sensors, temperature sensors, humidity sensors, rotation sensors, G sensors, timing sensors, air flow meters, electronic circuits, computer control units, voice coil motors, and semiconductor modules.

[0025] Thus, a curable perfluoropolyether gel composition, a cured perfluoropolyether gel formed by curing the composition, and electronic components sealed by the cured gel can be provided. The curable perfluoropolyether gel composition uses a perfluoropolyether compound that is not fully fluorinated and has a portion of hydrocarbon groups but no alkenyl groups as a plasticizer. It can suppress the leakage of plasticizers during heat resistance tests and has excellent chemical resistance, low temperature characteristics, and sealing properties, thus making it suitable for improving reliability.

[0026] The effects of the invention

[0027] As described above, the curable perfluoropolyether gel composition of the present invention provides a curable perfluoropolyether gel composition with excellent heat resistance, chemical resistance, low-temperature properties, and adhesion. In particular, by using a perfluoropolyether compound that is not fully fluorinated and has a portion of hydrocarbon groups but no alkenyl groups as a plasticizer, leakage of the plasticizer can be suppressed during heat resistance tests, thereby improving reliability. Attached Figure Description

[0028] Figure 1 This is a schematic diagram showing the air flow meter used in the thermal shock test. Detailed Implementation

[0029] As described above, the aim is to develop a fluorinated curable gel composition and an electronic component containing the cured product thereof. This fluorinated curable gel composition exhibits excellent heat resistance, chemical resistance, low-temperature properties, moisture resistance, and low permeability after curing. In particular, it can suppress the leakage of plasticizers during heat resistance tests. Therefore, it can be used to improve reliability even when applied to bonding, sealing, or coating materials for electronic components.

[0030] As a result of in-depth research conducted by the inventors in order to achieve the above-mentioned objectives, they discovered that the specific perfluoropolyether gel composition of the present invention provides a perfluoropolyether gel composition that, compared with conventional fluorinated gel compositions, can better suppress the leakage of plasticizers during heat resistance tests, thereby improving reliability, thus completing the present invention.

[0031] That is, the present invention provides a curable perfluoropolyether gel composition, a cured product thereof, and electronic components sealed by the cured product, wherein the curable perfluoropolyether gel composition contains the following components (A) to (D): (A) 10 to 90 parts by mass of an ingredient having at least two alkenyl groups in one molecule and containing -C in the main chain. a F 2a Perfluoropolyether compounds with repeating O- units and perfluoropolyether structures, wherein a is an integer from 1 to 6; (B) 10 to 90 parts by mass of a perfluoropolyether compound that does not have an alkenyl group in its molecule, selected from at least one of the compounds represented by the following general formulas (1) and (2), wherein the total of components (A) and (B) is 100 parts by mass. Rf 1 -C(=O)-NR1R2(1) R2R1N-C(=O)-Rf 2 -C(=O)-NR1R2(2) In equation (1), Rf 1 It is a monovalent perfluoropolyether group, in formula (2), Rf 2 It is a divalent perfluoropolyether group, where R1 in formula (1) and formula (2) is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group, and R2 is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group. (C) A curing effective dose of an organohydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule; (D) Catalyst amount for hydrogenation silylation reaction.

[0032] The present invention will be described in detail below, but the present invention is not limited thereto.

[0033] [(A) ingredient] The curable perfluoropolyether gel composition of the present invention includes component (A), which acts as the main agent (base polymer) of the curable perfluoropolyether gel composition of the present invention, having at least two alkenyl groups in one molecule and having a -C group in the main chain. a F 2a Perfluoropolyether compounds with a repeating O- unit (where a is an integer from 1 to 6) are perfluoropolyether compounds with a divalent perfluorooxyalkylene structure.

[0034] Here, as a perfluorooxyalkylene structure, it contains -C a F 2aMultiple repeating structures of oxyalkylene units represented by O- (where a in each unit is an integer from 1 to 6 independently), for example, structures represented by the following general formula (I) can be cited.

[0035] -(C a F 2a O) q - (I) In the formula, q is an integer from 50 to 200, preferably an integer from 50 to 190, and more preferably an integer from 50 to 170.

[0036] As each repeating structure -C constituting the perfluorooxyalkylene structure represented by the above formula (I) a F 2a O- (i.e., oxoalkylene unit), for example, the following structures can be cited. In addition, the above-mentioned perfluoroalkyl ether structures can be composed of one of these repeating structures alone, or a combination of two or more.

[0037] -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O- -C(CF3)2O-

[0038] The following structure is particularly preferred.

[0039] -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O-

[0040] The alkenyl group in the linear perfluoropolyether compound of component (A) preferably has 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and has a CH2=CH- structure at the end. Examples of preferred alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, and hexenyl groups with a CH2=CH- structure at the end, with vinyl and allyl groups being particularly preferred. This alkenyl group can be directly bonded to both ends of the perfluoropolyether structure constituting the main chain of the perfluoropolyether compound, particularly the divalent perfluorooxyalkylene structure, or it can be bonded via a divalent linking group, such as -CH2-, -CH2O-, -CH2OCH2-, or -Y-NR-CO-, where Y is -CH2- or a group represented by the following structural formula (Z). [Chemical Formula 5]

[0041] The group represented by the structural formula (Z) is a dimethylphenylmethylenesilyl group represented by the ortho, meta, or para position. R is a hydrogen atom, methyl, phenyl, or allyl. In addition, component (A) has at least two alkenyl groups in one molecule.

[0042] As component (A), examples of polyfluorodiene compounds represented by the following general formula (5) or (6) can be cited.

[0043] CH2=CH-(X) p -Rf 4 -(X') p -CH=CH2(5) CH2=CH-(X) p -Q-Rf 4 -Q-(X') p -CH=CH2(6) In the formula, X is independently -CH2-, -CH2O-, -CH2OCH2-, or -Y-NR 1 -CO-, where Y is -CH2- or a group represented by the following structural formula (Z), R 1 X' is a hydrogen atom, methyl, phenyl, or allyl group; X' is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR. 2 -Y'-, where Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 It can be a hydrogen atom, methyl, phenyl, or allyl.

[0044] [Chemical Formula 6]

[0045] The group represented by the structural formula (Z) is a dimethylphenylmethylenesilyl group represented by the ortho, meta, or para position. [Chemical Formula 7]

[0046] The group represented by the structural formula (Z') is a dimethylsilylphenylene group represented in the ortho, meta, or para positions.

[0047] Rf 4 It is a divalent perfluoropolyether structure (perfluorooxyalkylene structure), preferably derived from the above formula (I), i.e., -[C a F 2a O] q- indicates the structure. Q is a divalent hydrocarbon group with 1 to 15 carbon atoms, which may contain ether bonds, specifically an alkylene group, or an alkylene group that may contain ether bonds. p is independently 0 or 1.

[0048] The perfluoropolyether compound that is the component of this (A) is preferably a perfluoropolyether compound represented by the following general formula (3).

[0049] [Chemical Formula 8]

[0050] In the formula, X, X' and p are the same as above, r is an integer from 2 to 6, m and n are independent integers, m≥1, n≥1, 2≤m+n≤200.

[0051] Furthermore, of the total 100 parts by mass of component (A) and component (B) described later, the proportion of component (A) is 10 to 90 parts by mass, preferably 15 to 85 parts by mass. If this amount is less than 10 parts by mass, the penetration of the resulting composition may become extremely high and exhibit fluidity; if it exceeds 90 parts by mass, the penetration may become low and the composition may become hard, thus reducing its gel properties.

[0052] The perfluoropolyether compound of the above general formula (3) has a weight-average molecular weight (MAM) of 3,000 to 100,000, and particularly 4,000 to 50,000, in molecular weight distribution determination by gel permeation chromatography (GPC) with fluorinated solvents as eluents. If the MAM is 3,000 or higher, the swelling to gasoline and various solvents will be less. In particular, the swelling to gasoline is 6% or less, which meets the requirements for components requiring gasoline resistance. In addition, if the MAM is 100,000 or lower, the viscosity will not be too high, resulting in excellent workability and practicality.

[0053] Furthermore, the degree of polymerization (m+n) of the perfluoropolyether compound of the above general formula (3) can also be obtained in the following form: the number-average degree of polymerization or weight-average degree of polymerization converted to polyethylene in the molecular weight distribution determination by gel permeation chromatography (GPC) analysis using a fluorinated solvent as the developing solvent. In addition, these number-average degree of polymerization and number-average molecular weight can also be obtained from... 19 The ratio of the terminal structure to the repeating unit structure obtained from F-NMR spectroscopy is calculated.

[0054] As a specific example of a linear perfluoropolyether compound represented by general formula (3), a linear perfluoropolyether compound represented by the following formula can be cited.

[0055] [Chemical Formula 9]

[0056] [Chemical Formula 10]

[0057] Furthermore, in this invention, in order to adjust the perfluoropolyether compound of formula (3) to the desired weight-average molecular weight according to the purpose, the perfluoropolyether compound as described above can be subjected to a hydrosilylation reaction with an organosilicon compound containing two SiH groups in the molecule using conventional methods and conditions, and the product with extended chain length can be used as component (A). In addition, the perfluoropolyether compound of component (A) can be used alone or in combination with two or more.

[0058] [(B) Component] The (B) component of this invention is a perfluoropolyether compound that does not contain an alkenyl group in its molecule, but has an amide group and a hydrogen atom bonded to the nitrogen atom of the amide group at one or both ends of the molecular chain, or an unsubstituted or substituted monovalent hydrocarbon group that is not fully fluorinated (especially unsubstituted monovalent hydrocarbon groups other than alkenyl groups, such as alkyl, aryl, aralkyl, etc., or partially fluorinated monovalent hydrocarbon groups in which a portion of the hydrogen atom of the unsubstituted monovalent hydrocarbon group is replaced by a fluorine atom, or monovalent hydrocarbon groups in which the terminal end is substituted by a silalkylene group with a triorganosiloxy group). By using this perfluoropolyether compound as a plasticizer, a composition is provided that exhibits excellent chemical resistance and solvent resistance without impairing physical properties, and particularly, the plasticizer does not leak during heat resistance testing.

[0059] Component (B) is clearly distinguished from component (A) and components (C) and (E) described below in that it does not have an alkenyl or SiH group (hydrogen atom bonded to silicon atom) in its molecule that would exhibit the reactivity of hydrogenation silanization.

[0060] As component (B), a perfluoropolyether compound that does not have an alkenyl group in its molecule is used, which is selected from the group consisting of compounds represented by the following general formulas (1) and (2).

[0061] Rf 1 -C(=O)-NR1R2(1) R2R1N-C(=O)-Rf 2 -C(=O)-NR1R2(2) In equation (1), Rf 1 It is a monovalent perfluoropolyether group, in formula (2), Rf 2 It is a divalent perfluoropolyether group. In formulas (1) and (2), R1 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group, and R2 is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group.

[0062] Here, in the above general formulas (1) and (2), R1 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbon atoms that does not contain an alkenyl group, represented by R2. Examples of unsubstituted or substituted monovalent hydrocarbon groups with 1 to 15 carbon atoms that do not contain an alkenyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, etc., which are straight-chain, branched, or cyclic alkyl groups; benzene Aryl groups such as methyl, tolyl, and xylyl; unsubstituted monovalent hydrocarbon groups such as benzyl and phenylethyl; partially fluorinated monovalent hydrocarbon groups such as trifluoroethyl and trifluoropropyl whose hydrogen atoms are partially replaced by fluorine atoms; and monovalent hydrocarbon groups such as -C6H4-Si(CH3)2-CH2CH2-Si(CH3)2O-Si(CH3)3 whose terminal triorganosilicon alkylene groups are substituted with alkylene groups ...

[0063] Among them, preferred examples include ethyl, propyl, butyl, phenyl, -C6H4-Si(CH3)2-CH2CH2-Si(CH3)2O-Si(CH3)3, etc.

[0064] Furthermore, a perfluoropolyether compound can be used, wherein the Rf in the general formula (1) of component (B) is... 1 For F-[CF(CF3)CF2O] w -CF(CF3)- represents a perfluoropolyether compound, where w represents an integer from 1 to 200; or Rf in the general formula (2) of component (B) 2 For -CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)- represents a perfluoropolyether compound, where r is an integer from 2 to 6, m and n are independent integers, m≥1, n≥1, 2≤m+n≤200.

[0065] Specific examples of the general formula (1) as a component of (B) can be given, for example, the following general formula.

[0066] Additionally, the sum of the following w, r or m, n satisfies the above requirements. Ph represents phenyl.

[0067] F-[CF(CF3)CF2O] w -CF(CF3)-C(=O)-NH(CH2CH2CH3) F-[CF(CF3)CF2O] w -CF(CF3)-C(=O)-NH(CH2CH2CH2CH3) F-[CF(CF3)CF2O] w -CF(CF3)-C(=O)-NHPh F-[CF(CF3)CF2O] w -CF(CF3)-C(=O)-N(CH2CH3)2 F-[CF(CF3)CF2O] w -CF(CF3)-C(=O)-N(CH2CH2CH3)2 F-[CF(CF3)CF2O] w -CF(CF3)-C(=O)-N(CH3)Ph F-[CF(CF3)CF2O] w -CF(CF3)-C(=O)-NPh2 w is an integer from 1 to 200, preferably an integer from 2 to 190, more preferably an integer from 5 to 170, and even more preferably an integer from 10 to 150.

[0068] As a specific example of the general formula (2) of component (B), the following general formula can be given, for example.

[0069] Additionally, the sum of w, r or m, n below satisfies the above requirements. Ph represents phenyl, and Ph' represents phenylene.

[0070] (CH3CH2CH2)HN-C(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-NH(CH2CH2CH3) (CH3CH2CH2CH2)HN-C(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-NH(CH2CH2CH2CH3) PhHN-C(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-NHPh (CH3CH2)2N-C(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-N(CH2CH3)2 (CH3CH2CH2)2N-C(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-N(CH2CH2CH3)2 Ph(CH3)NC(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-N(CH3)Ph Ph2N-C(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-NPh2 (CH3)3SiO-Si(CH3)2-CH2CH2-Si(CH3)2-Ph'-NH-C(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-NH-Ph'-Si(CH3)2-CH2CH2-Si(CH3)2O-Si(CH3)3 r is an integer from 2 to 6, m and n are independent integers, m ≥ 1, n ≥ 1, preferably 3 ≤ m + n ≤ 190, more preferably 4 ≤ m + n ≤ 170, and even more preferably 5 ≤ m + n ≤ 150.

[0071] Furthermore, of the total 100 parts by mass of component (A) and component (B), the proportion of component (B) is 10 to 90 parts by mass, preferably 15 to 85 parts by mass, and more preferably 20 parts by mass or more. If the amount of this mixture is less than 10 parts by mass, the resulting cured product will become too hard and will not exhibit the properties of a gel; if it exceeds 90 parts by mass, the fluidity of the cured product may increase.

[0072] (B) The ingredients can be used alone or in combination of two or more.

[0073] [(C) Component] Component (C) is a component that acts as a crosslinking agent and / or chain length extender as component (A) or component (E) described later. This component (C) is an organohydropolysiloxane having at least two, preferably three or more, hydrogen atoms (hydrosilyl group denoted as SiH) bonded to silicon atoms in one molecule. Known organosilicon compounds can be cited as component (C), but are not particularly limited thereto.

[0074] Furthermore, from the viewpoint of compatibility with component (A) or component (E) described below, dispersibility, and uniformity of the cured gel, fluorinated organohydrogen polysiloxanes having one or more monovalent perfluoroalkyl, monovalent perfluorooxyalkyl, divalent perfluoroalkylene and / or divalent perfluorooxyalkylene in one molecule are suitable for use.

[0075] Examples of such monovalent or divalent fluorinated organic groups include perfluoroalkyl, perfluorooxyalkyl, perfluoroalkylene, and perfluorooxyalkylene, which are represented by the following formulas.

[0076] C g F 2g+1 - -C g F 2g - In the formula, g is an integer from 1 to 20, preferably an integer from 2 to 10.

[0077] [Chemical Formula 11]

[0078] In the formula, f is an integer from 1 to 200, preferably an integer from 1 to 100, and h is an integer from 1 to 3.

[0079] [Chemical Formula 12]

[0080] In the formula, i and j are integers greater than or equal to 1, preferably integers from 1 to 100, and the average of i+j is 2 to 200, preferably 2 to 100.

[0081] -(CF2O) d -(CF2CF2O) e -CF2- In the formula, d and e are integers from 1 to 50, preferably integers from 1 to 40.

[0082] In addition, these perfluoroalkyl, perfluorooxyalkyl, perfluoroalkylene, or perfluorooxyalkylene groups are preferably linked to silicon atoms by a divalent linking group. The divalent linking group can be an alkylene group, an arylene group, or a combination thereof, or groups such as ether oxygen atoms, amide bonds, carbonyl bonds, ester bonds, or diorganosilyl groups are interspersed between these groups. Examples of divalent linking groups with 2 to 12 carbon atoms are given, but are not limited to these.

[0083] -CH2CH2-、 -CH2CH2CH2-、 -CH2CH2CH2OCH2-、 -CH2CH2CH2-NH-CO-、 -CH2CH2CH2-N(Ph)-CO-、 -CH2CH2CH2-N(CH3)-CO-、 -CH2CH2CH2-N(CH2CH3)-CO-、 -CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO-、 -CH2CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO-、 -CH2CH2CH2-O-CO- In the formula, Ph represents phenyl and Ph' represents phenylene.

[0084] Furthermore, the monovalent or divalent fluorinated organic groups and monovalent substituents bonded to silicon atoms other than hydrogen atoms bonded to silicon atoms in the fluorinated organohydrogen polysiloxane of component (C) can be alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, and naphthyl; and aralkyl groups such as benzyl and phenethyl. Some or all of the hydrogen atoms of these groups are replaced by chlorine atoms, cyano groups, etc., such as chloromethyl, chloropropyl, cyanoethyl, etc., which have 1 to 20 carbon atoms, preferably 1 to 12, and are unsubstituted or substituted monovalent hydrocarbon groups.

[0085] The fluorinated organohydrogen polysiloxane, as component (C), can be cyclic, linear, branched, three-dimensional network, or a combination thereof. The number of silicon atoms in this fluorinated organohydrogen polysiloxane is not particularly limited, but is typically 2 to 60, preferably around 3 to 30.

[0086] Examples of compounds that have a monovalent or divalent fluorinated organic group and a silicon atom bonded to a hydrogen atom include the following. These compounds can be used alone or in combination of two or more. Furthermore, in the following formulas, Me represents methyl and Ph represents phenyl.

[0087] [Chemical Formula 13]

[0088] [Chemical Formula 14]

[0089] [Chemical Formula 15]

[0090] [Chemical Formula 16]

[0091] [Chemical Formula 17]

[0092] [Chemical Formula 18]

[0093] [Chemical Formula 19]

[0094] [Chemical Formula 20]

[0095] [Chemical Formula 21]

[0096] [Chemical Formula 22]

[0097] [Chemical Formula 23]

[0098] [Chemical Formula 24]

[0099] [Chemical Formula 25]

[0100] The amount of component (C) described above is the effective dosage for curing component (A) and component (E) described later, i.e., the effective curing dosage. In particular, relative to 1 mole of the total alkenyl groups present in component (A) and component (E) if present in this composition, the amount of hydrosilyl group (Si-H) in component (C) is preferably 0.2 to 4 moles, more preferably 0.5 to 3 moles. If the amount of hydrosilyl group (Si-H) is 0.2 moles or more, the degree of crosslinking is sufficient, and a cured product may not be obtained. In addition, if the amount of hydrosilyl group (Si-H) is 4 moles or less, foaming may occur during curing.

[0101] (C) The ingredients can be used alone or in combination of two or more.

[0102] [(D) component] The hydrosilylation catalyst (addition catalyst) of component (D) of the present invention is a catalyst that promotes the addition reaction between the alkenyl group in component (A) or the alkenyl group in component (E) described later, and the hydrosilylation group in component (C). This hydrosilylation catalyst is generally a compound of a noble metal (platinum group metals), and due to its high cost, platinum or platinum compounds, which are more readily available, are often used.

[0103] Photoactivated catalysts can be used as platinum catalysts when there are limitations in processes such as those involving thermally activated compounds or substrates with low heat resistance.

[0104] Examples of thermally activated platinum compounds include chloroplatinic acid or its complexes with olefins such as ethylene, complexes with vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. Other platinum group metal catalysts besides platinum compounds include rhodium, ruthenium, iridium, and palladium compounds, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO). 12 , IrCl(CO)(PPh3)2, Pd(PPh3)4, etc.

[0105] Photoactive hydrosilylation catalysts are activated, particularly by ultraviolet light irradiation at 300–400 nm, for example, (η 5 Compounds such as (-cyclopentadienyl)tri(σ-alkyl)platinum complexes and β-diketone platinum complexes can be cited. Specifically, examples include (methylcyclopentadienyl)trimethylplatinum (IV), (cyclopentadienyl)trimethylplatinum (IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum (IV), (cyclopentadienyl)dimethylethylplatinum (IV), (cyclopentadienyl)dimethylacetylplatinum (IV), (trimethylsilylcyclopentadienyl)trimethylplatinum (IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum (IV), (dimethylphenylsilyl) Trimethylcyclopentadienyl platinum (IV), trimethyl(acetylacetone) platinum (IV), trimethyl(3,5-heptanedione) platinum (IV), trimethyl(methylacetoacetic acid) platinum (IV), bis(2,4-pentanedione) platinum (II), bis(2,4-hexanedione) platinum (II), bis(2,4-heptanedione) platinum (II), bis(3,5-heptanedione) platinum (II), bis(1-phenyl-1,3-butanedione) platinum (II), bis(1,3-diphenyl-1,3-propanedione) platinum (II), bis(hexafluoroacetylacetone) platinum (II), etc.

[0106] When using these catalysts, if they are solid catalysts, they can be used in solid form, but in order to obtain a more uniform cured product, it is preferable to use a fluorinated polyether compound of component (A) in which the product is dissolved in a suitable solvent.

[0107] There are no particular limitations on the type of solvent used, as long as it can dissolve the catalyst. However, a solvent in which some of the hydrogen atoms of the hydrocarbon group are replaced by fluorine, or a mixture of a solvent in which some of the hydrogen atoms of the hydrocarbon group are replaced by fluorine and a solvent in which all of the hydrogen atoms of the hydrocarbon group are replaced by fluorine, is preferred in that it can make the catalyst more uniformly dispersed in the composition.

[0108] Solvents in which hydrogen is substituted for part of a hydrocarbon group are fluorinated, such as 1,3-bis(trifluoromethyl)benzene, 1,2-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, 1-methyl-3-(pentafluoroethyl)benzene, 1,1,1-trifluoro-3-[3-(trifluoromethyl)phenyl]prop-2-one, methyl 4-fluoro-3-(trifluoromethyl)benzoate, n-butyl heptafluorobutyrate, ethyl 3,5-bis(trifluoromethyl)benzoate, 2-methyl-5-(trifluoromethyl)benzaldehyde, and 2,3-dimethoxytrifluorotoluene.

[0109] In addition, solvents in which all hydrogen atoms of the hydrocarbon group are replaced by fluorine include, for example, octafluorotoluene, (1,1,2,3,3,3-hexafluoropropoxy)perfluorobenzene, pentafluoroethyl 2,2,2-trifluoroethyl ether, Fluorinert (manufactured by 3M), PF5060 (manufactured by 3M), and perfluoropolyether oligomers.

[0110] When the catalyst is used as a solution, the preferred mixing ratio of the linear polyfluorinated compound of component (A) to the catalyst solution is in the range of 100:0.01 to 1.00 (mass ratio). Adding more catalyst solution than this range may affect the physical properties of the cured product; conversely, adding less may result in poor dispersion of the composition. Therefore, appropriate adjustments can be made to bring the concentration of the catalyst solution within this mixing ratio range.

[0111] The amount of the catalyst for the hydrosilylation reaction can be set as the catalyst amount, but it is generally preferred to blend it at a ratio of 0.1 to 500 ppm (in terms of the mass of platinum group metals) relative to the total mass of component (A), component (E) and component (C) described later, and more preferably at a ratio of 0.1 to 100 ppm.

[0112] (D) The hydrogenation silylation catalyst can be used alone or in combination of two or more.

[0113] [(E) component] Component (E) is any component used in the curable perfluoropolyether gel composition of the present invention to reduce the crosslinking density and thus lower its modulus. Component (E) is a polyfluoromonoalkenyl compound having an alkenyl group in one molecule and a perfluoropolyether structure in the main chain. In particular, a polyfluoromonoalkenyl compound of the following general formula (4) is preferred.

[0114] Rf 3 -(X 2 ) p＇ -CH=CH2(4) In the formula, X 2 -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR 2 -Y 2 -, where Y 2 It is -CH2- or composed of the following structural formula (Z 2 The group represented by ) R 2 For hydrogen atoms, methyl, phenyl, or allyl groups; p' is 0 or 1; Rf 3 For the general formula F-[CF(CF3)CF2O] w＇ -CF(CF3)- represents the perfluoropolyether structure, where w' is represented by an integer from 1 to 300.

[0115] [Chemical Formula 26]

[0116] The structural formula (Z) 2 The group represented by ) is a dimethylphenylmethylenesilyl group represented in the ortho, meta, or para position.

[0117] As specific examples of polyfluoromonoolefin compounds represented by the above general formula (4), the following polyfluoromonoolefin compounds can be cited.

[0118] [Chemical Formula 27]

[0119] [Chemical Formula 28]

[0120] In the above formula, m is an integer from 1 to 200, and in particular an integer from 2 to 100.

[0121] When blending the polyfluorinated monoolefin compound of formula (4) above, the blending amount can be selected as follows: in the curable perfluoropolyether gel composition, relative to the total of 100 parts by mass of the above (A) component and (B) component in the composition, it is 0 to 100 parts by mass, preferably 1 to 50 parts by mass.

[0122] In addition, the polyfluoromonoolefin compounds of component (E) can be used alone or in combination with two or more.

[0123] [Other ingredients] In this composition, various blending agents may be added in any way other than components (A) to (E) mentioned above.

[0124] [(F)Component] Component (F) is a control agent (curing control agent) for the hydrogenation silylation reaction catalyst, and it can be any component. It can be added before heat curing, for example, when blending the above composition or when using the composition, to prevent the composition from thickening or gelling. Examples include alkynyl alcohols such as 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; or polymethylvinylsiloxane cyclic compounds, organophosphorus compounds, etc. By adding this component, the curing reactivity and storage stability can be appropriately maintained. Furthermore, component (F) can be used alone or in combination with two or more components.

[0125] The amount of component (F) is in the range of 0 to 5 parts by mass relative to the total of 100 parts by mass of components (A), (B) and (E), and preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.02 to 4 parts by mass. If the amount of component (F) is less than 5 parts by mass, the curability of the resulting composition may not be reduced.

[0126] (filler) Other inorganic fillers include, for example, untreated or hydrophobically treated fumigated silica (fumed silica, dry silica), precipitated silica (wet silica), colloidal silica, sol-gel silica, crystalline silica (quartz micron powder), fused silica, and crushed silica; iron oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, carbon black, etc. By adding these fillers, the hardness and mechanical strength of the gel-like cured product obtained from this composition can be adjusted. Hollow inorganic fillers or rubbery spherical fillers can also be added.

[0127] (Adhesive-enhancing agent) In addition, known adhesive agents containing epoxy groups, alkoxy groups, etc., can be added to impart adhesion.

[0128] (surfactant) Furthermore, to impart defoaming properties, known surfactants containing fluorine groups can also be added.

[0129] The amount of these blending ingredients used is arbitrary, depending on the characteristics of the resulting composition and the physical properties of the cured product.

[0130] [cured material] By curing the composition containing the above-mentioned components, a cured product can be formed that has excellent solvent resistance and chemical resistance, and can suppress the leakage of plasticizers during heat resistance tests, thus being suitable for improving reliability.

[0131] The formation of cured products using thermally active hydrogen silanization catalysts is carried out by conventional methods, such as injecting the composition into a suitable mold for curing or coating the composition onto a suitable substrate for curing. Curing can be easily carried out by heat treatment at a temperature of 60–150°C for about 30–180 minutes.

[0132] The formation of cured products using photoactive hydrogen silanization reaction catalysts allows the composition to be injected into a suitable mold or coated onto a suitable substrate and then cured by light.

[0133] Here, during curing, the irradiated light is preferably near-ultraviolet (hereinafter, sometimes simply referred to as ultraviolet), particularly in the region where the maximum peak wavelength in the emission spectrum is in the 300-400 nm region, and the irradiance at each wavelength in the wavelength region shorter than 300 nm is 5% or less of the irradiance at the maximum peak wavelength, preferably 1% or less, more preferably 0.1% or less, that is, the closer to 0, the better. If light is irradiated in the wavelength region shorter than 300 nm and has an irradiance greater than 5% of the irradiance at the maximum peak wavelength, decomposition of polymer end groups, partial decomposition of the catalyst, etc., may occur, and sufficient cured material may not be obtained.

[0134] The type of active light used to cure the photocurable fluoropolyether gel composition to obtain a gel is not particularly limited, but ultraviolet light of the wavelengths mentioned above is preferred. For obtaining good curability, the ultraviolet irradiance (illuminance), as the cumulative light intensity, is preferably set to 1,000 to 50,000 mJ / cm². 2 More preferably, it is set to 2,000–30,000 mJ / cm. 2 Further optimized, the value is set at 5,000–20,000 mJ / cm. 2If the ultraviolet irradiation (illuminance) is less than the above range, sufficient energy will not be obtained to activate the photoactive hydrosilylation catalyst in the composition, and a cured product with sufficient physical properties may not be obtained. On the other hand, if the ultraviolet irradiation (illuminance) exceeds the above range, the composition will be irradiated with more energy than required, which may cause decomposition of polymer end groups, partial deactivation of the catalyst, etc., and a sufficient cured product may not be obtained.

[0135] Ultraviolet (UV) irradiation can be light with multiple emission spectra or light with a single emission spectrum. Furthermore, the single emission spectrum can have a broad spectrum in the 300–400 nm region. Light with a single emission spectrum is light that has a peak (i.e., the maximum peak wavelength) in the 300–400 nm range, preferably in the 350–380 nm range. Examples of UV light sources for irradiation include UV light-emitting diodes (UV LEDs) and UV-emitting semiconductor lasers.

[0136] Examples of light sources that illuminate light with multiple emission spectra include metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, sodium lamps, low-pressure mercury lamps, high-pressure mercury lamps, and ultra-high-pressure mercury lamps; gas lasers such as nitrogen; liquid lasers based on organic pigment solutions; and solid-state lasers that incorporate rare earth ions into inorganic single crystals.

[0137] When the light has a peak in the wavelength region shorter than 300 nm in the emission spectrum, or when there is a wavelength in the wavelength region shorter than 300 nm with irradiance greater than 5% of the irradiance of the maximum peak wavelength in the emission spectrum (for example, when the emission spectrum spans a wide wavelength region), it is preferable to remove the light in the wavelength region shorter than 300 nm by using a filter. This allows the irradiance of each wavelength in the wavelength region shorter than 300 nm to be set to 5% or less of the irradiance of the maximum peak wavelength, preferably 1% or less, more preferably 0.1% or less, and even more preferably 0%. Furthermore, when multiple peaks exist in the wavelength region of 300–400 nm in the emission spectrum, the peak wavelength exhibiting the highest absorbance is taken as the maximum peak wavelength. There are no particular limitations on the filter as long as it cuts off wavelengths shorter than 300 nm; known filters can be used. For example, a 365 nm bandpass filter can be used. In addition, the illuminance and spectral distribution of ultraviolet light can be measured using a spectroradiometer, such as the USR-45D (Ushio Inc.).

[0138] There are no particular limitations on the light irradiation device; for example, point irradiation devices, surface irradiation devices, line irradiation devices, conveyor belt irradiation devices, and other irradiation devices can be used.

[0139] When the photocurable fluoropolyether gel composition is cured, the irradiation time is, for example, 1 to 300 seconds, preferably 10 to 200 seconds, more preferably 30 to 150 seconds, depending on the illuminance of the light used. After irradiation for 1 to 60 minutes, especially 5 to 30 minutes, the composition loses its fluidity and a gel solid can be obtained.

[0140] Furthermore, the ambient temperature during photocuring affects the curing time. That is, curing takes longer at lower temperatures and shorter at higher temperatures. To fully utilize the advantages of photocuring, the optimal curing temperature is 10–120°C. Below this range, curing takes longer, which is undesirable from a workability perspective; conversely, above this range, thermal degradation (heat distortion / heat discoloration) may occur depending on the substrate, which is also undesirable.

[0141] [Electronic Components] In addition, various control units, such as barometric pressure sensors, hydraulic sensors, temperature sensors, humidity sensors, rotation sensors, G-sensors, timing sensors, air flow meters, electronic circuits, voice coil motors, semiconductor modules, and computer control units, can be used as electronic components sealed by the cured product of this composition.

[0142] In addition, the cured material selected from any of these electronic components is preferably a gel composition, characterized by being cured by a hydrogen silanization reaction.

[0143] This is particularly relevant to gels cured using photoactivated catalysts. In other words, due to the complex shapes of electronic components in their packaging designs, there may be situations where light does not fully penetrate the gel composition even when exposed to it. This concern is addressed by hydrosilylation reactions with dark-area curing properties, where the dark areas are fully cured over time after light exposure.

[0144] Furthermore, the electronic components in this invention should be interpreted broadly, and therefore may also include electrical components, appliance components, etc.

[0145] Example

[0146] The present invention will now be specifically described with reference to embodiments and comparative examples, but the present invention is not limited to the embodiments described below. In addition, in the examples below, % represents mass%.

[0147] [Examples 1-4, Comparative Examples 1-4] The curable perfluoropolyether gel compositions shown in Table 1 were prepared using the following raw materials. The gel compositions using a thermally active hydrogen silanization catalyst were cured at 150°C for 60 minutes, while the gel compositions using a photoactive hydrogen silanization catalyst were cured at a wavelength of 365 nm and a concentration of 100 mW / cm². 2The UV irradiation was applied at 23°C for 90 seconds to cure the material, and after standing at 23°C for 24 hours, the penetration, solvent resistance, dynamic viscoelasticity, DSC, thermal shock, and leakage tests of each cured product were performed using the following methods. The results are recorded in Table 1.

[0148] raw material (A) Linear perfluoropolyether compounds Bifunctional perfluoropolyether (perfluoropolyether 1) [Chemical Formula 29]

[0149] (B) Perfluoropolyether compounds (b-1) Perfluoropolyether 2 (average molecular weight: 4,400) F-[CF(CF3)CF2O] 24 -CF(CF3)-C(=O)-N(CH2CH3)2 (w=24)

[0150] (b-2) Perfluoropolyether 3 (average molecular weight: 16,830) Ph(CH3)NC(=O)-CF(CF3)-[OCF2CF(CF3)] m -O(CF2)2O-[CF(CF3)CF2O] n -CF(CF3)-C(=O)-N(CH3)Ph (m+n=98)

[0151] (b-3) Perfluoropolyether 4 (average molecular weight: 4,700) CF3O-(CF2CF2CF2O) b -C2F5 (where b=27)

[0152] (b-4) Perfluoropolyether 5 (average molecular weight: 4,100) CF3O-[(CF2O) d (CF2CF(CF3)O) e ]-CF3 (d+e=25, d=1, e=24)

[0153] (C) Organohydrosiloxanes [Chemical Formula 30]

[0154] (D) Addition reaction catalyst: (d-1)CAT-PL-50T (trade name manufactured by Shin-Etsu Chemical Co., Ltd., platinum compound 1) (d-2) (methylcyclopentadienyl)trimethylplatinum(IV) / hexafluorom-xylene = 5% / 95% (platinum compound 2)

[0155] (E) Monofunctional perfluoropolyether compounds (perfluoropolyether 6) [Chemical Formula 31]

[0156] (F) Curing control agent: Ethynylcyclohexanol

[0157] Penetration Measurement Samples were prepared and cured under the following conditions: the obtained compositions were placed in glass petri dishes with a diameter of φ30×14mm. For Example 1, the curing temperature was 150°C for 60 minutes. For Examples 2-4 and Comparative Examples 1-4, the curing temperature was 365nm and the curing time was 100mW / cm². 2 The UV irradiation was applied at 23°C for 90 seconds to cure the material, followed by standing at 23°C for 24 hours, and then the penetration was measured. Additionally, the penetration of the cured material was measured using a quarter-cone according to ASTM D-1403.

[0158] Solvent resistance test (weight change) Samples were prepared and cured under the following conditions: 3g of each composition was filled into a 32φ×15mm glass container. Example 1 was cured at 150°C for 60 minutes, and Examples 2-4 and Comparative Examples 1, 3-4 were cured at a wavelength of 365nm and a curing temperature of 100mW / cm². 2 The UV irradiation was applied at 23°C for 90 seconds to cure the material, and then it was left to stand at 23°C for 24 hours. Finally, it was immersed in xylene at 25°C for 7 days, and the weight change rate before and after immersion was measured.

[0159] Dynamic viscoelasticity measurement Using a dynamic viscoelasticity measuring device, Example 1 involved a thickness of 1.0 mm, a diameter of 20 mm, a frequency of 1 Hz, a strain of 10%, and measurement and curing at 150°C for 60 minutes. After cooling, the resin modulus (storage modulus G') was measured again at 25°C under the same conditions. Examples 2-4 and Comparative Examples 1, 3-4 were measured at a wavelength of 365 nm and a wavelength of 100 mW / cm². 2 The resin was cured under UV irradiation at 25°C for 90 seconds and then left to stand at 25°C for 2 hours. The resin modulus (storage modulus G') at 25°C was then measured.

[0160] Glass Turn change Point measurement For the cured products of compositions other than Comparative Example 2, the glass transition point was determined by DSC (Differential Scanning Calorimetry) in the range of -130°C to 25°C (heating rate 5°C / min).

[0161] thermal shock test Fill all compositions other than Comparative Example 2 into Figure 1 In the air flow meter 1 shown, after degassing and curing under reduced pressure, the cycle is performed 1000 times, with one cycle being -30°C (1 hour) and 150°C (1 hour). No abnormalities such as peeling from the substrate are observed (○), and peeling is observed (×). Furthermore, the air flow meter 1 includes a detection section 3, and each composition 2 is filled to cover a portion of the detection section 3.

[0162] Leakage test Samples were prepared and cured under the following conditions: the obtained compositions were placed in glass petri dishes with a diameter of φ30×14mm. For Example 1, the curing temperature was 150°C for 60 minutes. For Examples 2-4 and Comparative Examples 1, 3-4, the curing temperature was 365nm and the curing time was 100mW / cm². 2 The material was cured by UV irradiation at 23°C for 90 seconds and then left to stand at 23°C for 24 hours. Following this, a heat resistance test was conducted at 150°C for 100 hours. After the test, the surface of the cured material was checked by touching it with a finger; areas without oil adhesion were marked as ○, and areas with oil adhesion were marked as ×.

[0163] [Table 1]

[0164] As shown in Table 1, it can be seen that if the gels used in Examples 1 to 4 of the curable perfluoropolyether gel composition of the present invention are employed, the adhesion obtained through thermal shock testing is good and no plasticizer leakage occurs. Furthermore, the cured products obtained in the above examples have an appropriate penetration and flexibility suitable for bonding electronic components, exhibit sufficient solvent resistance, and have a low glass transition temperature, thus possessing excellent low-temperature characteristics. Moreover, because the resin modulus has an appropriate range, the shape retention and adhesion to the substrate as a gel are excellent.

[0165] In contrast, in Comparative Example 1, where the essential component (A) of the present invention was in excess, the resin modulus was high and the adhesion was reduced. In Comparative Example 2, where the essential component (B) was in excess, the resin did not solidify but flowed, and no shape retention as a gel was observed. Furthermore, in Comparative Examples 3 and 4, where the essential component (B) used a fully fluorinated perfluoropolyether, leakage of plasticizer was confirmed on the surface of the gel after the heat resistance test.

[0166] As can be seen from the above, if it is the present invention, it will become a fluorinated curable gel composition, which has excellent heat resistance, chemical resistance, low temperature characteristics, and adhesion after curing. In particular, by using a perfluoropolyether compound that is not fully fluorinated but has some hydrocarbon groups and no alkenyl groups as a plasticizer, the leakage of plasticizer can be suppressed during the heat resistance test, thus improving reliability.

[0167] This instruction manual includes the following methods.

[0168] [1]: A curable perfluoropolyether gel composition, characterized in that it contains the following components (A) to (D): (A) 10 to 90 parts by mass of an ingredient having at least two alkenyl groups in one molecule and containing -C in the main chain. a F 2a Perfluoropolyether compounds with repeating O- units and perfluoropolyether structures, wherein a is an integer from 1 to 6; (B) 10 to 90 parts by mass of a perfluoropolyether compound that does not have an alkenyl group in its molecule, selected from at least one of the compounds represented by the following general formulas (1) and (2), wherein the total of components (A) and (B) is 100 parts by mass. Rf 1 -C(=O)-NR1R2(1) R2R1N-C(=O)-Rf 2 -C(=O)-NR1R2(2) In equation (1), Rf 1 It is a monovalent perfluoropolyether group, in formula (2), Rf 2 It is a divalent perfluoropolyether group, where R1 in formula (1) and formula (2) is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group, and R2 is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 15 carbons without an alkenyl group. (C) A curing effective dose of an organohydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule; (D) Catalyst amount for hydrogenation silylation reaction.

[0169] [2]: The curable perfluoropolyether gel composition according to [1] is characterized in that the component (A) is a perfluoropolyether compound represented by the following general formula (3): [Chemical Formula 32] ; In the formula, X is -CH2-, -CH2O-, -CH2OCH2-, or -Y-NR 1 -CO-, where Y is -CH2- or a group represented by the following structural formula (Z), R 1X' is a hydrogen atom, methyl, phenyl, or allyl group; X' is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR. 2 -Y'-, where Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 It can be a hydrogen atom, methyl, phenyl, or allyl; p is independently 0 or 1; r is an integer from 2 to 6; m and n are independent integers, m≥1, n≥1, 2≤m+n≤200; [Chemical Formula 33] ; [Chemical Formula 34] .

[0170] [3]: The curable perfluoropolyether gel composition according to [1] or [2] is characterized in that Rf in general formula (1) of component (B) is 1 For F-[CF(CF3)CF2O] w -CF(CF3)- represents a perfluoropolyether compound, where w represents an integer from 1 to 200; or Rf in the general formula (2) of component (B) 2 For -CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)- represents a perfluoropolyether compound, where r is an integer from 2 to 6, m and n are independent integers, m≥1, n≥1, 2≤m+n≤200.

[0171] [4]: The curable perfluoropolyether gel composition according to any one of [1] to [3] further comprises, as component (E), a polyfluoromonoolefin compound represented by the following general formula (4): Rf 3 -(X 2 ) p＇ -CH=CH2(4) In the formula, X 2 -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR 2 -Y 2 -, where Y 2 It is -CH2- or composed of the following structural formula (Z 2 () represents a group, [Chemical Formula 35] ; The structural formula (Z) 2The group represented by ) is a dimethylphenylmethylenesilyl group represented in the ortho, meta, or para position; R 2 For hydrogen atoms, methyl, phenyl, or allyl groups, p' is 0 or 1, Rf 3 For the general formula F-[CF(CF3)CF2O] w＇ -CF(CF3)- represents the perfluoropolyether structure, where w' is represented by an integer from 1 to 300.

[0172] [5]: The curable perfluoropolyether gel composition according to any one of [1] to [4] is characterized in that the (D) component is a catalyst activated by heat or light.

[0173] [6]: A perfluoropolyether gel curing product, characterized in that the perfluoropolyether gel curing product is obtained by curing the curable perfluoropolyether gel composition described in any one of [1] to [5].

[0174] [7]: The perfluoropolyether gel curing material according to [6] is characterized in that the perfluoropolyether gel curing material is used to seal any electronic component selected from the group consisting of: barometric pressure sensor, hydraulic sensor, temperature sensor, humidity sensor, rotation sensor, G sensor, timing sensor, air flow meter, electronic circuit, computer control unit, voice coil motor and semiconductor module.

[0175] [8]: An electronic component, characterized in that the electronic component is sealed by the perfluoropolyether gel cured material described in [6].

[0176] [9]: The electronic component according to [8] is characterized in that the electronic component is selected from any one of the group consisting of: barometric pressure sensor, hydraulic sensor, temperature sensor, humidity sensor, rotation sensor, G sensor, timing sensor, air flow meter, electronic circuit, computer control unit, voice coil motor and semiconductor module.

[0177] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples; any technical solution having a substantially similar structure and achieving the same effect as the technical concept described in the claims of this invention is included within the technical scope of this invention.

Claims

1. A curable perfluoropolyether gel composition characterized in that, contains the following (A) component to (D) component: (A) 10 to 90 parts by mass of an ingredient having at least two alkenyl groups in one molecule and containing -C in the main chain. a F 2a Perfluoropolyether compounds with repeating O- units and perfluoropolyether structures, wherein a is an integer from 1 to 6; (B) 10 to 90 parts by mass of a perfluoropolyether compound having no alkenyl group in the molecule selected from at least one of the compounds represented by the following general formulae (1) and (2), wherein the total of the (A) component and the (B) component is 100 parts by mass; Rf 1 -C(=O)-NR1R2 (1) R2R1N-C(=O)-Rf 2 -C(=O)-NR1R2 (2) In formula (1), Rf 1 is a monovalent perfluoropolyether group, and in formula (2), Rf 2 is a divalent perfluoropolyether group, R1in formula (1) and formula (2) is a hydrogen atom or a carbon number 1 to 15 unsubstituted or substituted monovalent hydrocarbon group not containing an alkenyl group, and R2is a carbon number 1 to 15 unsubstituted or substituted monovalent hydrocarbon group not containing an alkenyl group. (C) a solidification effective amount of an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule; (D) a catalyst amount of a hydrosilylation reaction catalyst.

2. The curable perfluoropolyether gel composition according to claim 1, characterized in that, The (A) component is a perfluoropolyether compound represented by the following general formula (3): [Chemical Formula 1] ； wherein X is -CH2-, -CH2O-, -CH2OCH2-, or -Y-NR 1 -CO-, wherein Y is -CH2- or a group represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group; X' is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR 2 -Y'- wherein Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group; p is independently 0 or 1; r is an integer of 2 to 6; m, n are integers independent of each other, m > 1, n > 1, 2 < m + n < 200; [Chemical Formula 2] ； [Chemical Formula 3] 。 3. The curable perfluoropolyether gel composition according to claim 1, wherein Rf in the general formula (1) of the component (B) 1 F-[CF(CF3)CF2O]n-CF(CF3)-CF2- wherein n represents an integer of 1 to 200; or w F-[CF(CF3)CF2O]n-CF(CF3)-CF2- wherein n represents an integer of 1 to 200; or Rf in the general formula (2) of the component (B) 2 -CF(CF3)-[OCF2CF(CF3)] m -O(CF2) r O-[CF(CF3)CF2O] n -CF(CF3)- represents a perfluoropolyether compound, wherein r is an integer of 2 to 6; m, n are integers independent of each other; m > 1, n > 1, 2 < m + n < 200.

4. The curable perfluoropolyether gel composition of claim 1, wherein, Further, as the (E) component, a polyfluoromonovinyl compound represented by the following general formula (4) is included: Rf 3 -(X 2 ) p＇ -CH=CH2 (4) wherein X 2 is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR 2 -Y 2 - wherein Y 2 is -CH2- or a group represented by the following structural formula (Z 2 ), [Chemical Formula 4] ； The group represented by the structural formula (Z 2 ) is a dimethylphenylsilyl group represented by the ortho-, meta- or para-position. R 2 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group; p' is 0 or 1; Rf 3 is a perfluoropolyether structure represented by the general formula F-[CF(CF3)CF2O] w＇ -CF(CF3)-, wherein w' represents an integer from 1 to 300.

5. The curable perfluoropolyether gel composition according to claim 1, wherein The (D) component is a catalyst activated by heat or light.

6. A perfluoropolyether gel cured product, characterized by, The perfluoropolyether gel cured product is obtained by curing the curable perfluoropolyether gel composition according to any one of claims 1 to 5.

7. The perfluoropolyether gel solidified product according to claim 6, characterized by, The perfluoropolyether gel cured product is used for sealing any electronic component selected from the group consisting of: a gas pressure sensor, a liquid pressure sensor, a temperature sensor, a humidity sensor, a rotation sensor, a G sensor, a timing sensor, an air flow meter, an electronic circuit, a computer control unit, a voice coil motor, and a semiconductor module.

8. An electronic component, characterized by The electronic component is sealed by the perfluoropolyether gel cured product according to claim 6.

9. The electronic component according to claim 8, characterized by The electronic component is selected from any one of the group consisting of: a gas pressure sensor, a liquid pressure sensor, a temperature sensor, a humidity sensor, a rotation sensor, a G sensor, a timing sensor, an air flow meter, an electronic circuit, a computer control unit, a voice coil motor, and a semiconductor module.

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