Adhesive composition, die bonding material, protective encapsulant or coating agent, and electrical-electronic component

Abstract

The present invention relates to an adhesive composition of perfluoropolyether system, which contains: (A) a linear perfluoropolyether compound having 2 or more alkenyl groups in one molecule, a number average molecular weight of 2000 or more, and a mass reduction rate of 1% or less when heated at 150°C for 1 hour; (B) a fluorine-containing organohydrogen polysiloxane compound having 1 or more fluorine-containing organic groups, not containing an epoxy group and a trialkoxysilyl group, a number average molecular weight of 1000 to 4000, and a mass reduction rate of 20% or less when heated at 150°C for 1 hour; (C) a platinum group metal compound; (D) organohydrogen polysiloxane compounds each having 1 or more epoxy groups and / or trialkoxysilyl groups bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and a number average molecular weight of 700 or more, and forming a fluorine-containing elastomer cured product which is less likely to cause contamination of surrounding parts caused by exhaust gas generated upon heat curing.

Description

Technical Field

[0001] This invention relates to perfluoropolyether-based adhesive compositions, chip bonding materials containing the adhesive compositions, protective sealants or coatings, and electrical-electronic components such as automotive sensor components, printing and copying devices, or fuel cell components having cured products of the aforementioned adhesive compositions. The perfluoropolyether-based adhesive compositions form fluorinated elastomer cured products that exhibit minimal contamination of surrounding components due to exhaust gases generated during heat curing, strong adhesion to various substrates such as metals and plastics, and excellent solvent resistance, chemical resistance, heat resistance, low-temperature characteristics, low moisture permeability, and electrical properties after curing. Background Technology

[0002] Curable fluoroelastomer compositions utilizing the addition reaction of alkenyl and hydrosilyl groups are known. A composition possessing self-adhesive properties has been proposed by further adding an organopolysiloxane having hydrosilyl and epoxy and / or trialkoxysilyl groups as a third component (adhesion enhancer) to this composition (Patent Document 1: Japanese Patent Application Publication No. 9-95615). This composition can be cured by short-time heating, and the resulting cured product (fluoroelastomer cured product) exhibits excellent solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, and electrical properties, thus making it suitable for adhesive applications in various industrial fields where these properties are required.

[0003] However, it has been pointed out that gaseous impurities (generally referred to as "venting") are generated during the heat curing of this composition, which contaminate surrounding components and cause adverse effects. For example, if this composition is used as a sealant in the head portion of an inkjet printer, the venting (gaseous low-molecular-weight fluorinated compounds) generated during its heat curing contaminates the ink discharge path and the vicinity of the discharge port, causing problems with ink discharge performance. In the manufacturing process of automotive sensors, etc., when used as a material for fixing chips on a substrate such as resin (chip bonding material), contamination caused by venting contaminates the gold pads on the chip, resulting in the inability to perform wire bonding. Regarding this venting, it is believed that in addition to the low-polymerization-degree perfluoropolyether compound in the main agent (base polymer) contained in the composition and the fluorinated organohydrosiloxane as a crosslinking agent, low-molecular-weight components such as fluorinated organic compounds or non-fluorinated organic compounds mixed as adhesion enhancers are generated by volatilization from the composition before the curing reaction is completed upon heating. As a means of suppressing pollution of surrounding parts caused by exhaust, adhesive compositions using fluorinated organic compounds or non-fluorinated organic compounds as components of adhesiveness improvers with a molecular weight of 2000 or more and very low volatile components at 105°C are known (Patent Document 2: Japanese Patent No. 4582287).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 9-95615

[0007] Patent Document 2: Japanese Patent No. 4582287 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] If a perfluoropolyether adhesive composition is used, consisting only of components with a molecular weight of 2000 or higher, venting is reduced. Furthermore, the viscosity of high molecular weight components other than the base polymer is readily reflected in the overall viscosity of the adhesive composition. For example, if a high molecular weight fluorinated component with a viscosity lower than that of the base polymer (a perfluoropolyether compound containing alkenes) is blended, the resulting perfluoropolyether adhesive composition will have a low viscosity. Conversely, if a high molecular weight fluorinated component with a viscosity higher than that of the base polymer is blended, the resulting perfluoropolyether adhesive composition will have a high viscosity. Furthermore, the fluorinated elastomer cured by curing a perfluoropolyether adhesive composition containing these high molecular weight fluorinated components other than the base polymer is easily cured and has a soft (low hardness) finish. In chip bonding applications, when using this perfluoropolyether adhesive composition to fix sensor chips onto a substrate, the fluorinated elastomer cured from this composition is soft. Due to the softness of the cured fluorinated elastomer, the chip cannot be firmly held, and wire bonding sometimes becomes difficult. By adding inorganic fillers, it is possible to achieve high viscosity of the perfluoropolyether adhesive composition and improve the physical properties of the cured fluorinated elastomer, but sometimes it is difficult to achieve adhesion to metals, resins, etc.

[0010] For the reasons mentioned above, it is preferable that the molecular weight of some or all of the components in the perfluoropolyether adhesive composition, other than the base polymer, is relatively low, and that the perfluoropolyether adhesive composition causes minimal contamination of surrounding parts due to venting during curing.

[0011] Therefore, the present invention was made in view of the above-mentioned actual situation, and its object is to provide a perfluoropolyether-based adhesive composition, a chip bonding material containing the adhesive composition, a protective sealant or coating agent containing the adhesive composition, and an electrical-electronic component having the cured product of the adhesive composition. The perfluoropolyether-based adhesive composition forms a fluorinated elastomer cured product that has low contamination of surrounding components caused by exhaust gas generated during heat curing, and firmly bonds to various substrates such as metals and plastics. Furthermore, it exhibits excellent solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, and electrical properties after curing.

[0012] Methods for solving problems

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by using a base polymer with a number average molecular weight of 2000 or more and a low molecular weight component that causes venting, and a crosslinking agent with a number average molecular weight of 1000 or more and less than 4000, a perfluoropolyether adhesive composition is obtained that produces almost no contamination of surrounding parts caused by venting during heat curing, even if the number average molecular weight of the fluorinated organic compound or non-fluorinated organic compound used as an adhesive enhancer is not 2000 or more (specifically, even if the adhesive enhancer is a low molecular weight component of about 700 to 2000).

[0014] Therefore, the present invention provides the following adhesive composition, chip bonding material comprising the adhesive composition, protective sealant or coating comprising the adhesive composition, and electrical-electronic components having the cured adhesive composition. [1]

[0016] Adhesive composition comprising:

[0017] (A) A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a number-average molecular weight of 2000 or more: 100 parts by mass of (A) when (A) is heated alone at 150°C for 1 hour, the mass reduction rate of (A) is less than 1%.

[0018] (B) A fluorinated organohydrogen polysiloxane compound having two or more hydrogen atoms bonded to silicon atoms in one molecule, and having one or more fluorinated organic groups, without epoxy groups or trialkoxysilyl groups, and having a number average molecular weight of 1000 or more and 4000 or less: the amount of which is such that, relative to 1 mole of alkenyl groups in component (A), the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 2.5 moles, and the mass reduction rate of component (B) when heated alone at 150°C for 1 hour is less than 20%.

[0019] (C) Platinum group metal compounds: 0.1–1000 ppm relative to the mass of component (A), expressed in platinum group metal atomic conversions.

[0020] (D) An organohydrogen polysiloxane compound having one or more hydrogen atoms bonded to silicon atoms and epoxy and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon and oxygen atoms, with a number average molecular weight of 700 or more: in such amounts that, relative to 1 mole of alkenyl groups in component (A), the number of hydrogen atoms bonded to silicon atoms in component (D) is 0.005 to 1.5 moles. [2]

[0022] According to the adhesive composition of [1], wherein component (A) is a linear perfluoropolyether compound represented by the following general formula (1).

[0023] [Chemistry 1]

[0024]

[0025] [In the formula, A] 1 Each is independently selected from any one of the following groups: a divalent organic group with 1 to 4 carbon atoms that may contain ether or amide bonds; a group represented by the following general formula (2); and a group represented by the following general formula (3).

[0026] [Chemistry 2]

[0027]

[0028] (where Y) 1 Y is a hydrogen atom, methyl, ethyl, or phenyl. 2 It can be a hydrogen atom, methyl, ethyl, or trifluoromethyl, and o can be an integer from 1 to 6. The * symbol indicates a bond with Rf. 1 Bonding.

[0029] B is a carbon atom or a silicon atom, X 1 Each is independent, at least two are alkenyl groups, and the others are X groups. 1 For hydrogen atoms (limited to the case where B is a carbon atom) or methyl groups, Rf 1 It is a divalent perfluoropolyether group. [3]

[0031] According to the adhesive composition of [1] or [2], wherein the mass reduction rate of component (A) when heated alone at 150°C for 1 hour is less than 0.5%. [4]

[0033] The adhesive composition according to any one of [1] to [3], wherein the alkenyl content of component (A) is 0.002 to 0.3 mol / 100g. [5]

[0035] The adhesive composition according to any one of [1] to [4], wherein component (B) is a fluorinated organohydrogen polysiloxane compound represented by the following general formula (4).

[0036] [Chemistry 3]

[0037]

[0038] [In the formula, R] 1For unsubstituted or halogenated monovalent hydrocarbon groups, L 1 The following general formula (5) represents a monovalent fluorinated organic group containing a monovalent perfluoropolyether group, which can be bonded to silicon atoms via a divalent linking group, where w1 is an integer from 0 to 50, x1 is an integer from 2 to 50, y1 is an integer from 1 to 50, and w1+x1+y1 is an integer satisfying a number average molecular weight of 1000 to 4000. The repeating units of () can be arranged randomly.

[0039] E-(C4F8O) c -(C3F6O) d -(C2F4O) e -(CF2O) f -C g F 2g -(5)

[0040] (E is a fluorine atom or a perfluorooxyalkyl group with 1 to 6 carbon atoms; c, d, e, and f are each independent integers from 0 to 20, where 2 ≤ c + d + e + f ≤ 20; g is an integer from 1 to 3. The repeating units in the above parentheses can be arranged randomly.) [6]

[0042] The adhesive composition according to any one of [1] to [5], wherein component (D) has one or more monovalent perfluoroalkyl or monovalent perfluorooxyalkyl groups bonded to silicon atoms via a divalent linking group comprising at least one of nitrogen, carbon and oxygen atoms in one molecule. [7]

[0044] The adhesive composition according to any one of [1] to [6] further comprises, relative to 100 parts by weight of component (A), 0.010 to 10 parts by weight of carboxylic anhydride (E). [8]

[0046] Chip bonding material comprising an adhesive composition according to any one of [1] to [7]. [9]

[0048] The chip bonding material described in [8] is used for vehicle sensors.

[10]

[0050] Protective sealant or coating agent comprising an adhesive composition according to any one of [1] to [7].

[11]

[0052] The protective sealant or coating agent described in

[10] is used in printing, copying devices or fuel cells.

[12]

[0054] Electrical-electronic components having a cured product of an adhesive composition according to any one of [1] to [7].

[13]

[0056] According to

[12] , the electrical-electronic component is an article for an on-board sensor in which a sensor chip is fixed by a cured adhesive composition.

[14]

[0058] According to

[12] , the electrical-electronic component is a component for printing, copying devices or fuel cells that uses a cured adhesive composition as a protective seal or coating layer.

[0059] The effects of the invention

[0060] The adhesive composition according to the present invention can form a cured product with minimal contamination of surrounding parts caused by exhaust gas generated during heating and curing, strong adhesion to various substrates such as metals and plastics, and excellent solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, and electrical properties after curing. Attached Figure Description

[0061] Figure 1 The diagram shows the appearance of the sensor chip during the contamination confirmation test during heat curing in Example 1. (a) is a photograph of the appearance before the contamination confirmation test during heat curing, and (b) is a photograph of the appearance after the contamination confirmation test during heat curing.

[0062] Figure 2 The diagram shows the appearance of the sensor chip during the contamination confirmation test during heat curing in Comparative Example 1. (a) is a photograph of the appearance before the contamination confirmation test during heat curing, and (b) is a photograph of the appearance after the contamination confirmation test during heat curing. Detailed Implementation

[0063] The present invention will now be described in more detail.

[0064] [Adhesive Composition]

[0065] The adhesive composition of the present invention is characterized by containing the following components (A), (B), (C) and (D).

[0066] [(A) ingredient]

[0067] The linear perfluoropolyether compound of component (A) used in the adhesive composition of the present invention has at least two alkenyl groups in one molecule and a number average molecular weight of 2000 or more. The mass reduction rate of component (A) when heated alone at 150°C for 1 hour is less than 1%. Preferably, it has a divalent perfluoroalkyl ether structure in the main chain as shown in the general formula (1) described below, and functions as a main agent (base polymer) in the adhesive composition of the present invention.

[0068] In this invention, the degree of polymerization (or molecular weight) of linear polyfluorinated compounds, reflecting the number of repeating perfluorooxyalkylene units constituting the main chain of the perfluoropolyether structure, can be determined, for example, using a fluorinated solvent as the elution solvent, as the number-average degree of polymerization (or number-average molecular weight) converted from polystyrene in gel permeation chromatography (GPC) analysis. Furthermore, the number-average degree of polymerization (or number-average molecular weight) of the aforementioned linear polyfluorinated compounds can also be determined by… 19 Calculated by F-NMR.

[0069] It should be noted that component (A) above is a substance with a number-average molecular weight of 2000 or more, obtained by the synthesis method described in Japanese Patent Application Publication No. 9-95615, and particularly preferably a substance with a number-average molecular weight of 4000 or more. This linear perfluoropolyether compound with a number-average molecular weight of less than 2000 tends to volatilize more during heat curing, causing contamination of surrounding components, and is therefore not preferred. It should be noted that the upper limit of this number-average molecular weight is only about 50,000 or less, and particularly about 20,000 or less.

[0070] In addition, regarding the linear perfluoropolyether compound of component (A), the mass reduction rate of component (A) when heated at 150°C for 1 hour (heat treatment at 150°C) is less than 1%, preferably less than 0.5%.

[0071] When the mass reduction rate of the (A) linear perfluoropolyether compound caused by the 150°C heat treatment is greater than 1% (especially 1.0%), exhaust gases are generated from the adhesive composition containing it during heat curing, causing contamination.

[0072] The mass reduction rate can be determined using the following method. Weigh the tare weight (W1) of a clean aluminum pan using a precision balance (reading limit 0.0001 mg). Next, take a sample from the aluminum pan and weigh the pan containing the sample using a precision balance (W2). Place the aluminum pan containing the sample in a thermostat at 150°C (atmosphere) for 1 hour. After heating, remove the aluminum pan from the thermostat and allow it to cool naturally in a desiccator. After natural cooling, weigh the aluminum pan containing the sample using a precision balance (W3). Calculate the mass reduction rate of the sample using the following formula.

[0073] {(W3-W1) / (W2-W1)}×100 (unit: %)

[0074] W1: Mass of aluminum disc (g)

[0075] W2: Mass of aluminum disc + mass of sample before heating (g)

[0076] W3: Mass of aluminum disc + mass of heated sample (g)

[0077] The method for determining the rate of mass reduction is the same for components (B) and (D) described later.

[0078] It should be noted that in the linear perfluoropolyether compounds represented by general formula (1) described below, the perfluoropolyether compounds with low degree of polymerization contained therein sometimes inevitably contain at least components with a number average molecular weight of less than 2000, which may be the cause of exhaust.

[0079] Therefore, component (A) with low molecular weight components removed can be prepared by performing, for example, the following operation 1 as a pretreatment on the linear perfluoropolyether compound represented by general formula (1) described below.

[0080] [Operation 1]

[0081] It is obtained by subjecting a linear perfluoropolyether compound, preferably a linear perfluoropolyether compound represented by general formula (1) as described below, to a pressure of 1330 Pa or less, preferably 665 Pa or less, and a temperature of 100 to 300°C, preferably 150 to 250°C, for at least 1 hour, preferably 5 hours or more under reduced pressure.

[0082] (A) The preferred component is a linear perfluoropolyether compound having the structure shown in the following general formula (1). In this invention, "linear" means that the repeating units of the perfluoropolyether structure constituting the main chain, namely the perfluorooxyalkylene units, are bonded (linked) to each other in a linear form, and each perfluorooxyalkylene unit may have a branched structure such as [OCF2CF(CF3)] unit.

[0083] [Chemistry 4]

[0084]

[0085] [In the formula, A] 1 Each is independently selected from any one of the following groups: a divalent organic group with 1 to 4 carbon atoms that may contain ether or amide bonds; a group represented by the following general formula (2); and a group represented by the following general formula (3).

[0086] [Chemistry 5]

[0087]

[0088] (where Y) 1 Y is a hydrogen atom, methyl, ethyl, or phenyl atom. 2 It can be a hydrogen atom, methyl, ethyl, or trifluoromethyl, and o can be an integer from 1 to 6. It should be noted that the bond terminator marked with an asterisk (*) indicates a bond with Rf. 1 Bonding.

[0089] B is a carbon atom or a silicon atom, X 1 Each is independent, and there are 6 X's in the molecule (3 at each end of the molecular chain). 1 In the group, at least two are alkenyl groups, and the others are X groups. 1 For hydrogen atoms (limited to the case where B is a carbon atom) or methyl groups, Rf 1 It is a divalent perfluoropolyether group.

[0090] In the above general formula (1), A 1 It is any one of the following groups: a divalent organic group with 1 to 4 carbon atoms that may contain ether bonds or amide bonds, a group represented by the following general formula (2), and a group represented by the general formula (3).

[0091] [Chemistry 6]

[0092]

[0093] (where Y) 1 Y is a hydrogen atom, methyl, ethyl, or phenyl. 2 It can be a hydrogen atom, methyl, ethyl, or trifluoromethyl, and o can be an integer from 1 to 6. It should be noted that the bond terminator marked with an asterisk (*) indicates a bond with Rf. 1 Bonding (the same applies below).

[0094] As A 1 Examples include -CH2-*, -OCH2-*, -CH2CH2OCH2-*, -CH2-NH-CO-*, -CH2CH2-NH-CO-*, -CH2-NCH3-CO-*, and groups represented by the following general formulas (2A), (2B), (2C), (3A), (3B), and (3C), with groups represented by general formula (2A) or (3A) being preferred. It should be noted that Me represents methyl and Et represents ethyl.

[0095] [Chemistry 7]

[0096]

[0097] In the above general formula (1), B is a carbon atom or a silicon atom.

[0098] In addition, there are 6 X atoms in the molecule (i.e., 3 at each end of the molecular chain). 1In this process, at least two (specifically, three X's exist at each end of the molecular chain) are present. 1 In each group, at least one is an alkenyl group, preferably with 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and having a CH2=CH- structure at the end. Examples include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, etc., with vinyl and allyl being preferred. In X 1 When B is not an alkenyl group, it becomes either a hydrogen atom or a methyl group when B is a carbon atom, and it becomes a methyl group when B is a silicon atom.

[0099] In the above general formula (1), Rf 1 It is a divalent perfluoropolyether group containing -C a F 2a Repeating units of O- (where a is an integer from 1 to 6.) can be listed, for example, groups represented by the following formula (6).

[0100] -(C a F 2a O) x - (6)

[0101] (In formula (6), a is an integer from 1 to 6, and x is an integer from 5 to 600, preferably an integer from 10 to 400, and more preferably an integer from 30 to 200.)

[0102] As given by the above equation -C a F 2a The repeating unit represented by O can be, for example, the unit represented by the following formula.

[0103] -CF2O-

[0104] -CF2CF2O-

[0105] -CF2CF2CF2O-

[0106] -CF(CF3)CF2O-

[0107] -CF2CF2CF2CF2O-

[0108] -CF2CF2CF2CF2CF2CF2O-

[0109] Of these, the unit represented by the following formula is particularly suitable.

[0110] -CF2O-

[0111] -CF2CF2O-

[0112] -CF2CF2CF2O-

[0113] -CF(CF3)CF2O-

[0114] It should be noted that the repeating units in the divalent perfluoropolyether group can be composed of one of these alone, or a combination of two or more of them.

[0115] In addition, the above-mentioned divalent perfluoropolyether group preferably includes the structure of the following formulas (7) to (11).

[0116] [Chemistry 8]

[0117]

[0118] -CF2CF2-(OCF2CF2CF2) z -OCF2CF2- (10)

[0119] -C k′ F 2k′ -(OC a″ F 2a″ OC a″′ F 2a″′ ) z′ -OC k′ F 2k′ - (11)

[0120] (In the formula, D is a fluorine atom or a trifluoromethyl group, p, q, and r are integers satisfying p≥0, q≥0, 0≤p+q≤200, especially 2≤p+q≤150 and 0≤r≤6 (when p+q=0, 1≤r≤6), and k, a', s, t, and u are integers satisfying 1≤k≤3, 2≤a'≤6, 0≤s≤100, 0≤t≤100, 2≤s+t≤200, 0≤u≤6, especially 2≤s+t≤150, 0≤ The integers u≤4 and 2≤s+t+u≤150, v and w are integers satisfying 1≤v≤100, 1≤w≤100, and 2≤v+w≤150, z is an integer satisfying 1≤z≤200, k', a”, and a”' are integers satisfying 1≤k'≤3, 1≤a”≤6, 1≤a”'≤6, and a”≠a”', and z' is an integer satisfying 1≤z'≤200. The repeating units in equation (9) can be arranged randomly.

[0121] In the above general formula (1), as Rf 1 Specific examples can be illustrated by groups represented by the following formulas (12) to (21).

[0122] [Chemistry 9]

[0123]

[0124] -CF₂O-(C₂F₄O) n1 -CF2- (16)

[0125] -CF2--(OC2F4) n -(OCF2) m -O-CF2- (17)

[0126]

[0127] -CF2CF2--(OCF2CF2CF2) z -OCF2CF2- (19)

[0128] -(C2F4O) n2 -CF2CF2- (20)

[0129] -CF2--(OC2F4OC4F8) z -OCF2- (21)

[0130] (In equation (12) above, p, q, and r are each integers satisfying p≥0, q≥0, 0≤p+q≤200, especially 2≤p+q≤150, and 0≤r≤6. In equations (13), (14), (15), (17), and (18) above, n is an integer from 1 to 100, m is an integer from 1 to 100, and n+m is an integer from 2 to 200. In equation (16) above, n1 is an integer from 2 to 200. In equation (19) above, z is an integer from 1 to 200. In equation (20) above, n2 is an integer from 2 to 200. In equation (21) above, z' is an integer from 1 to 200. The repeating units of () in equations (17) and (18) can be arranged randomly.)

[0131] As for component (A) represented by the above general formula (1), in the case that B is a silicon atom, the substances represented by the following formulas (22) to (35) are particularly suitable. It should be noted that Me is methyl and Et is ethyl in the formulas.

[0132] [Chemistry 10]

[0133]

[0134] (m is an integer from 1 to 100, n is an integer from 1 to 100, and m+n is an integer from 2 to 200.)

[0135] [Chemistry 11]

[0136]

[0137] (m is an integer from 1 to 100, n is an integer from 1 to 100, and m+n is an integer from 2 to 200.)

[0138] [Chemistry 12]

[0139]

[0140] (m is an integer from 1 to 100, n is an integer from 1 to 100, and m+n is an integer from 2 to 200.)

[0141] [Chemistry 13]

[0142]

[0143] (m is an integer from 1 to 100, n is an integer from 1 to 100, and m+n is an integer from 2 to 200.)

[0144] [Chemistry 14]

[0145]

[0146] (m is an integer from 1 to 100, n is an integer from 1 to 100, and m+n is an integer from 2 to 200.)

[0147] As component (A) represented by the above general formula (1), in the case that B is a carbon atom, the substance represented by the following formula is suitable.

[0148] [Chemistry 15]

[0149] CH2=CH-CH2-O-CH2-CF2-(OC2F4) n -(OCF2) m -O-CF2-CH2-O-CH2-CH=CH2

[0150]

[0151] (m is an integer from 1 to 100, n is an integer from 1 to 100, and m+n is an integer from 2 to 200.)

[0152] The alkenyl content in the linear perfluoropolyether compound of formula (1) above is preferably 0.002 to 0.3 mol / 100g, more preferably 0.008 to 0.12 mol / 100g. When the alkenyl content in the linear perfluoropolyether compound is less than 0.002 mol / 100g, the degree of crosslinking becomes insufficient, which may result in poor curing, and is therefore not preferred. When the alkenyl content exceeds 0.3 mol / 100g, the mechanical properties of the cured product as a rubber elastomer may be impaired, and is therefore not preferred.

[0153] When the compositions of the present invention are used for sealing, casting, coating, impregnation, etc., they also possess suitable physical properties in the cured product. Therefore, it is desirable that the viscosity (23°C) of the linear perfluoropolyether compound of component (A) is in the range of 40–100,000 mPa·s, more preferably 50–50,000 mPa·s, and even more preferably 60–20,000 mPa·s. 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 type, rheometer, etc.) (as in the examples).

[0154] Regarding component (A), these linear perfluoropolyether compounds can be used alone or in combination of two or more.

[0155] [(B) Component]

[0156] The (B) component used in the adhesive composition of the present invention is a fluorinated organic hydrogen polysiloxane compound having two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule, having one or more fluorinated organic groups, not containing epoxy groups or trialkoxysilyl groups, and having a number average molecular weight of 1000 or more and 4000 or less. When the (B) component is heated alone at 150°C for 1 hour, the mass reduction rate of the (B) component is less than 20%, and it functions as a crosslinking agent or chain extender for the (A) component.

[0157] Here, the number average molecular weight of component (B) is 1000 to 4000, preferably 1000 to 2500. Fluorinated organohydrogen polysiloxane compounds with a number average molecular weight of less than 1000, if present in the adhesive composition, will cause contamination as exhaust gases during heat curing, and are therefore undesirable. On the other hand, fluorinated organohydrogen polysiloxane compounds with a number average molecular weight greater than 4000 tend to have a viscosity that is easily reflected in the adhesive composition, making it difficult to bring the viscosity value of the adhesive composition within a specific range, and are therefore also undesirable.

[0158] Furthermore, regarding the fluorinated organohydrogen polysiloxane compound of component (B), the mass reduction rate of component (B) when heated alone at 150°C for 1 hour (heat treatment at 150°C) is 20% or less, preferably 15% or less, and more preferably 8% or less. When the mass reduction rate of this fluorinated organohydrogen polysiloxane compound is greater than 20%, venting may occur from the adhesive composition containing it during heat curing, causing contamination of surrounding components, which is therefore undesirable.

[0159] Furthermore, for the adhesive composition of the present invention, it is desirable that the mass reduction rate of component (A) when heated alone at 150°C for 1 hour is less than 1% (particularly 1.0%), and the mass reduction rate of component (B) when heated alone at 150°C for 1 hour is less than 20%. This suppresses the generation of venting gas during the heat curing of the adhesive composition of the present invention, preventing contamination.

[0160] Furthermore, from the viewpoints of compatibility with component (A), dispersibility, and uniformity after curing, in the above-mentioned component (B), as a fluorinated organic group in the molecule, it is more preferable to have one or more perfluoroalkyl, perfluorooxyalkyl (monovalent perfluoropolyether group), perfluoroalkylene or perfluorooxyalkylene (divalent perfluoropolyether group) in one molecule.

[0161] In particular, component (B) preferably has a monovalent perfluoropolyether group represented by the following general formula (5).

[0162] E-(C4F8O) c -(C3F6O) d -(C2F4O) e -(CF2O) f -C g F 2g -(5)

[0163] (E is a fluorine atom or a perfluorooxyalkyl group with 1 to 6 carbon atoms, c, d, e, and f are each independent integers from 0 to 20, where 2 ≤ c + d + e + f ≤ 20, and g is an integer from 1 to 3. The repeating units in the above parentheses can be arranged randomly.)

[0164] In the above general formula (5), when c+d+e+f is less than 2, component (B) sometimes evaporates as exhaust gas during the heating and curing of the adhesive composition, causing contamination, which is not preferred. On the other hand, when c+d+e+f is greater than 20, it is difficult to make the viscosity value of the adhesive composition converge within a specific range, which is also not preferred.

[0165] Examples of monovalent perfluoropolyether groups represented by the above general formula (5) include the following groups.

[0166] [Chemistry 16]

[0167]

[0168] (In the formula, b is an integer from 1 to 6, in formula (36), e' is an integer from 2 to 20, in formulas (37) to (40), d' is an integer from 2 to 20, in formula (41), e and f are each an integer from 0 to 20, e+f is an integer from 2 to 20, and in formula (42), c' is an integer from 2 to 20.)

[0169] The aforementioned monovalent perfluoropolyether group is bonded to a silicon atom in a (fluorinated) organohydrogen polysiloxane compound, and a divalent linking group may be present between the monovalent perfluoropolyether group and the silicon atom. The divalent linking group is any one of a divalent organic group having 1 to 6 carbon atoms that may contain an ether bond or an amide bond, a group represented by the following general formula (43A), and a group represented by the general formula (43B).

[0170] [Chemistry 17]

[0171]

[0172] (where Y) 3 h1 is a hydrogen atom, methyl, ethyl, or phenyl group, h1 is 0 or 1, and h2 is an integer from 1 to 6. It should be noted that the bonding end marked with * indicates bonding to a monovalent perfluoropolyether group represented by the above general formula (5) (the same applies below).

[0173] Examples of such divalent linking groups include -CH2-*, -OCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, -(CH2)3-NCH3-CO-*, and groups represented by the following general formulas, among which -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, and any one of the groups represented by the following general formulas are preferred. It should be noted that in the following formulas, Me represents a methyl group.

[0174] [Chemistry 18]

[0175]

[0176] (B) The siloxane backbone of the fluorinated organohydrogen polysiloxane compound can be cyclic, linear, branched, etc., and is preferably a fluorinated organohydrogen polysiloxane compound having a cyclic siloxane backbone. In particular, as the fluorinated organohydrogen polysiloxane compound of component (B), a compound represented by the following general formula (4) can be used.

[0177] [Chemistry 19]

[0178]

[0179] (where R is in the formula) 1 For unsubstituted or halogenated monovalent hydrocarbon groups, L 1This refers to a monovalent perfluoropolyether group represented by the above general formula (5), which can be bonded to silicon atoms via the aforementioned divalent linking groups. w1 is an integer from 0 to 50, preferably an integer from 0 to 20; x1 is an integer from 2 to 50, preferably an integer from 3 to 20; and y1 is an integer from 1 to 50, preferably an integer from 1 to 20. Furthermore, w1+x1+y1 is an integer satisfying the number average molecular weight of 1000 to 4000 as described above, preferably 3≤w1+x1+y1≤53, more preferably 4≤w1+x1+y1≤20, and even more preferably 4≤w1+x1+y1≤10. The repeating units in the above () can be arranged randomly.

[0180] As mentioned above, R 1 The unsubstituted or halogenated monovalent hydrocarbon group is preferred, preferably a monovalent hydrocarbon group with 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group with 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 phenylethyl; and substituted monovalent hydrocarbon groups formed by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine. Methyl is particularly preferred.

[0181] (B) The number-average molecular weight of component (B) can be obtained through... 1 H-NMR and 19 The calculation is performed by F-NMR determination. When the structures of each component within () in the above general formula (4) and the structural units contained in the above general formula (5) are clearly defined, the compound represented by general formula (5) is analyzed. 1 H-NMR determination and 19 F-NMR determination allows the number-average molecular weight to be calculated from the integral values ​​of each component in formula (4) and the integral values ​​of each repeating unit in formula (5).

[0182] As a component (B) having a fluorinated organic group, the following compounds can be listed as preferred examples. It should be noted that in the following formulas, Me represents a methyl group.

[0183] [Chemistry 20]

[0184]

[0185] (In the formula, c' is an integer from 4 to 20.)

[0186] [Chemistry 21]

[0187]

[0188] (In the formula, c' is an integer from 4 to 20.)

[0189] (B) The Si-H base content of component (B) is preferably 0.05 to 0.8 mol / 100g, and particularly preferably 0.1 to 0.6 mol / 100g.

[0190] The amount of component (B) mentioned above is the effective amount for curing component (A). Typically, for every 1 mole of vinyl, allyl, cycloalkenyl, or other alkenyl groups contained in component (A), the amount of silyl groups (≡Si-H groups) in component (B) is 0.1 to 2.5 moles, preferably 0.2 to 2 moles. If there is too little silyl group (≡Si-H group), the degree of crosslinking will be insufficient, and sometimes a cured product cannot be obtained. Conversely, if there is too much, foaming may occur during curing.

[0191] It should be noted that the total amount of Si-H groups in component (B) and component (D) described below is typically 0.105 to 4 moles of alkenyl groups relative to 1 mole in component (A), preferably 0.21 to 3 moles, and more preferably 0.41 to 2.5 moles.

[0192] It should be noted that, as a suitable embodiment, the fluorinated organohydrogen polysiloxane compound that functions as a crosslinking agent or chain extender in component (A) of the composition of the present invention, uses a fluorinated organohydrogen polysiloxane compound with a mass reduction rate of 20% or less. This can be achieved by using a cyclic fluorinated organohydrogen polysiloxane compound with a mass reduction rate of 15% or less (100% by mass or less), particularly 75% by mass or less (0 to 75% by mass), and further 55% by mass or less (0 to 55% by mass) in proportion to the cyclic fluorinated organohydrogen polysiloxane compound with a mass reduction rate greater than 15% (preferably 16 to 20%, more preferably around 16 to 18%), in combination with a fluorinated organohydrogen polysiloxane compound having a linear siloxane structure. This fluorinated organohydrogen polysiloxane compound, having a linear siloxane structure, is clearly distinguished from the adhesive-imparting organohydrogen polysiloxane compound described later in component (D) by the absence of functional groups such as epoxy groups and trialkoxysilyl groups in its molecule that contribute to adhesion. Examples of preferred embodiments of this fluorinated organohydrogen polysiloxane compound with a linear siloxane structure include the compounds shown below. It should be noted that in the following formula, Me represents methyl.

[0193] [Chemistry 22]

[0194]

[0195] (In the formula, i is an integer from 3 to 20, and c' is an integer from 2 to 20.)

[0196] (B) Components may be used alone or in combination of two or more. It should be noted that the fluorinated organohydrogen polysiloxane compound of component (B) does not have functional groups such as epoxy groups and trialkoxysilyl groups in its molecule that can contribute to adhesion, and is clearly distinguished from the adhesive-improving agent of component (D) described later, namely the organohydrogen polysiloxane compound.

[0197] [(C) Component]

[0198] The adhesive composition of the present invention uses component (C) as a platinum group metal compound. It is a hydrosilylation catalyst, which promotes the addition reaction of the alkenyl group in component (A) with the hydrosilylation groups in components (B) and (D). This hydrosilylation catalyst is generally a precious metal compound, which is expensive; therefore, platinum or platinum compounds, which are relatively easy to obtain, are often used.

[0199] Examples of platinum compounds include chloroplatinic acid or its complexes with alkenes such as ethylene, complexes with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. Other platinum group metal compounds besides platinum compounds include rhodium, ruthenium, iridium, and palladium compounds, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO). 12 Examples include IrCl(CO)(PPh3)2 and Pd(PPh3)4. It should be noted that in the above formulas, Ph represents phenyl groups.

[0200] When used as these catalysts, they can be used in solid form when they are solid catalysts. In order to obtain a more uniform cured product, it is preferable to use the product obtained by dissolving chloroplatinic acid and the complex in a suitable solvent and make it compatible with the linear perfluoropolyether compound of component (A).

[0201] The amount of component (C) used can be the amount of catalyst, for example, preferably 0.1 to 1000 ppm (in platinum group metal atom conversion) relative to the mass of component (A), more preferably 1 to 500 ppm. Component (C) can be used alone or in combination of two or more.

[0202] [(D) component]

[0203] Regarding component (D) used in the adhesive composition of the present invention, it functions as an adhesive enhancer by compounding to enable the composition of the present invention to fully exhibit self-adhesiveness. It is an organohydrogen polysiloxane compound having one or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule and epoxy and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon and oxygen atoms, and having a number average molecular weight of 700 or more.

[0204] More preferably, in component (D) above, each molecule also has one or more monovalent perfluoroalkyl or monovalent perfluoropolyether groups (perfluoroalkyl groups) bonded to silicon atoms via divalent linking groups comprising at least one of nitrogen, carbon, and oxygen atoms, preferably bonded to silicon atoms via divalent linking groups comprising nitrogen and carbon atoms or via divalent linking groups comprising nitrogen, carbon, and oxygen atoms. Such monovalent perfluoroalkyl or monovalent perfluoropolyether groups may be the same as the groups shown in component (B) above. In addition, the divalent linking group connecting the monovalent perfluoroalkyl or monovalent perfluoropolyether group to the silicon atom may also be the same as the groups shown in component (B) above.

[0205] The number average molecular weight of component (D) above is preferably 700 to 4000, more preferably 900 to 2000. If this organohydrogen polysiloxane compound with a number average molecular weight of less than 700 is present in the adhesive composition, it may sometimes cause contamination as exhaust gas during its heat curing, and it may sometimes be difficult to formulate a sufficient amount to exhibit self-adhesion to various substrates, therefore it is not preferred. On the other hand, organosiloxanes with a number average molecular weight greater than 4000 have a significantly increased viscosity, making formulation difficult, therefore they are also not preferred.

[0206] (D) The siloxane skeleton of the organohydrogen polysiloxane compound can be any of the following: cyclic, linear, branched, etc., or it can be a mixture of two or more of them.

[0207] As component (D), the organohydrogen polysiloxane compound may be a substance represented by the following general formula.

[0208] [Chemistry 23]

[0209]

[0210] (where R is in the formula) 2 For unsubstituted or halogenated monovalent hydrocarbon groups, L 2 M is a monovalent perfluoropolyether group bonded to silicon atoms via a divalent linking group, as shown below. M is an epoxy or trialkoxysilyl group bonded to silicon atoms via a carbon atom or a carbon and oxygen atom, as shown below. w2 is preferably an integer satisfying 0 ≤ w2 ≤ 50, more preferably an integer satisfying 0 ≤ w2 ≤ 20; x2 is preferably an integer satisfying 1 ≤ x2 ≤ 50, more preferably an integer satisfying 1 ≤ x2 ≤ 20; y2 is preferably an integer satisfying 0 ≤ y2 ≤ 50, more preferably an integer satisfying 1 ≤ y2 ≤ 20; z2 is preferably an integer satisfying 1 ≤ z2 ≤ 50, more preferably an integer satisfying 1 ≤ z2 ≤ 20. Furthermore, w2 + x2 + y2 + z2 is an integer satisfying a number-average molecular weight of 700 to 4000 as described above. The repeating units in the above () can be arranged randomly.

[0211] As mentioned above, R 2 The unsubstituted or halogenated monovalent hydrocarbon group is preferably a monovalent hydrocarbon group with 1 to 10 carbon atoms that does not contain aliphatic unsaturated bonds, and more preferably a monovalent hydrocarbon group with 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 phenylethyl; and substituted monovalent hydrocarbon groups formed by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine. Methyl is particularly preferred.

[0212] The above L 2 It is a monovalent perfluoropolyether group bonded to silicon atoms via a divalent linking group, preferably a group represented by the following general formula (44).

[0213] -Z-Rf 3 (44)

[0214] In formula (44), Z is any one of the following groups: a divalent organic group with 1 to 6 carbon atoms that may contain ether or amide bonds, a group represented by the following general formula (45), and a group represented by the general formula (46).

[0215] [Chemistry 24]

[0216]

[0217] (where Y) 4 It can be a hydrogen atom, methyl, ethyl, or phenyl group, where j1 is an integer from 1 to 6. It should be noted that the bonding end marked with an asterisk (*) indicates bonding to a monovalent perfluoropolyether group (the same applies below).

[0218] Rf 3 It is a monovalent perfluoropolyether group.

[0219] Examples of Z include -CH2-*, -OCH2-*, -CH2OCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -CH2-NH-CO-*, -(CH2)3-NH-CO-*, and groups represented by the following general formulas (45A), (45B), and (46A), wherein -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, and groups represented by general formulas (45A), (45B), or (46A) are preferred. It should be noted that in the following formulas, Me represents a methyl group.

[0220] [Chemistry 25]

[0221]

[0222] In the above general formula (44), Rf3 It is a monovalent perfluoropolyether group, represented by the following general formula (47).

[0223] E1-(C4F8O) c1 -(C3F6O) d1 -(C2F4O) e1 -(CF2O) f1 -C g1 F 2g1 -(47)

[0224] (E1 is a perfluoroalkyl group with 1 to 6 carbon atoms, and c1, d1, e1, and f1 are each independent integers from 0 to 20, such that 2 ≤ c1 + d1 + e1 + f1 ≤ 20. g1 is an integer from 1 to 3. The repeating units in the above parentheses can be arranged randomly.)

[0225] Examples of monovalent perfluoropolyether groups represented by the above general formula (47) include the following groups.

[0226] [Chemistry 26]

[0227]

[0228] (In the formula, b1 is an integer from 1 to 6, in formula (48), e1' is an integer from 2 to 20, in formulas (49) to (52), d1' is an integer from 2 to 20, in formula (53), e1 and f1 are each integers from 0 to 20, e1+f1 is 2 to 20, and in formula (54), c1' is an integer from 2 to 20.)

[0229] The M above represents an epoxy or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. Specifically, the following groups can be listed.

[0230] [Chemistry 27]

[0231]

[0232] (where R is in the formula) 3 This refers to a divalent hydrocarbon group (methylene, ethylene, propylene, etc., cyclohexene, oxoethylene, oxopropylene, oxobutylene, etc., preferably -(CH2)3OCH2-*' (the *' indicates bonding with an epoxy group)) that can contain an oxygen atom.

[0233] -R 4 -Si(OR 5 )3

[0234] (where R is in the formula) 4R represents a divalent hydrocarbon group (such as methylene, ethylene, propylene, etc.) with 1 to 10 carbon atoms, especially 1 to 4 carbon atoms. 5 Independently representing a monovalent hydrocarbon group (methyl, ethyl, propyl, butyl, etc.) with 1 to 8 carbon atoms, especially 1 to 4 carbon atoms.

[0235] [Chemistry 28]

[0236]

[0237] (where R is in the formula) 6 R is a hydrogen atom or a methyl group. 7 (Independently representing monovalent hydrocarbon groups with 1 to 8 carbon atoms, especially 1 to 4 carbon atoms (such as alkyl groups like methyl, ethyl, propyl, and butyl), where 1 represents an integer from 2 to 10.)

[0238] (D) The number-average molecular weight of component (D) can be obtained through... 1 H-NMR and 19 F-NMR determination and calculation. Given that the structures of each component within the parentheses in the above general formula (5) representing component (D) are clearly defined, the structural units contained in the above general formula (5) are determined by... 1 H-NMR determination and 19 F-NMR determination allows the number-average molecular weight to be calculated from the integral values ​​of each component in the above general formula () representing component (D) and the integral values ​​of each repeating unit shown in general formula (5).

[0239] (D) The organohydrogen polysiloxane compound can be obtained by a partial addition reaction of an organohydrogen polysiloxane having three or more hydrogen atoms bonded to silicon atoms in one molecule (Si-H groups) with a compound containing aliphatic unsaturated groups such as vinyl and allyl, and epoxy and / or trialkoxysilane groups, and further, if necessary, a compound containing aliphatic unsaturated groups and perfluoroalkyl or perfluorooxyalkyl groups, according to conventional methods. It should be noted that the number of aliphatic unsaturated groups needs to be less than the number of Si-H groups.

[0240] In the manufacture of organohydrogen polysiloxane compounds of component (D), the target substance can be separated after the reaction is completed, or a mixture in which only unreacted substances and addition reaction catalysts have been removed can be used.

[0241] Organohydropolysiloxane compounds that are component (D) are specifically exemplified by compounds shown in the following structural formulas. It should be noted that these compounds can be used alone or in combination of two or more. It should be noted that in the following formulas, Me represents a methyl group.

[0242] [Chemistry 29]

[0243]

[0244] (In the formula, x2' is 2 or 3, and d1' is an integer from 2 to 20.)

[0245] [Chemistry 30]

[0246]

[0247] (In the formula, x2' is 2 or 3, and d1' is an integer from 2 to 20.)

[0248] [Chemistry 31]

[0249]

[0250] (In the formula, x2' is 1 or 2, and d1' is an integer from 2 to 20.)

[0251] [Chemistry 32]

[0252]

[0253] (In the formula, z2' is 2 or 3, and d1' is an integer from 2 to 20.)

[0254] [Chemistry 33]

[0255]

[0256] (In the formula, y2' is 2 or 3, and d1' is an integer from 2 to 20.)

[0257] The Si-H base content of component (D) is preferably 0.06 to 0.6 mol / 100g.

[0258] Regarding the amount of component (D), the amount of hydrogen atoms bonded to silicon atoms in component (D) is 0.005 to 1.5 moles relative to 1 mole of alkenyl group in component (A), preferably 0.01 to 1.0 moles, and more preferably 0.05 to 0.5 moles. If the amount of hydrogen atoms bonded to silicon atoms in component (D) is less than 0.005 moles relative to 1 mole of alkenyl group in component (A), sufficient adhesion cannot be obtained. If the amount of hydrogen atoms bonded to silicon atoms in component (D) exceeds 1.5 moles relative to 1 mole of alkenyl group in component (A), the flowability of the composition deteriorates, the physical strength of the cured product decreases, and curing is often hindered, therefore this is not preferred.

[0259] [(E) component]

[0260] Component (E) is a carboxylic anhydride, which is an optional component used to enhance the adhesive-imparting ability of component (D) and promote the emergence of self-adhesiveness in the cured product obtained by curing the composition of the present invention. As this component, a substance used as a curing agent for epoxy resins can be used.

[0261] Carboxylic anhydrides that are components (E) include, for example, carboxylic anhydrides that are solid at 23°C. Specifically, the following compounds can be listed. It should be noted that in the following formulas, Me represents a methyl group.

[0262] [Chemistry 34]

[0263]

[0264] Additionally, the carboxylic anhydride as component (E) may be a cyclic organopolysiloxane (i.e., a fluorinated organopolysiloxane modified carboxylic anhydride compound) represented by the following general formula, having a hydrogen atom directly bonded to a silicon atom in one molecule, a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group that may have an oxygen atom or a nitrogen atom, and a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group.

[0265] [Chemistry 35]

[0266]

[0267] In the above formula, T' is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent hydrocarbon group that may have an oxygen or nitrogen atom. Examples of T's that bond with component (B) above are listed. 1 The same groups. These groups were introduced from the perspective of compatibility, dispersibility and uniformity after curing of component (A).

[0268] Additionally, R 21 For unsubstituted or substituted monovalent hydrocarbon groups, examples of R groups mentioned above can be listed. 1 The same group is preferred, such as methyl or ethyl.

[0269] Furthermore, t”' is an integer from 1 to 6, preferably an integer from 2 to 5; u”' is an integer from 1 to 4, preferably an integer from 1 to 3; v”' is an integer from 1 to 4, preferably an integer from 1 to 3; and t”'+u”'+v”' is an integer from 4 to 10, preferably an integer from 4 to 8. Wherein, ((H)(R 21 (SiO) unit, ((T')(R) 21 SiO) unit, and ((X')(R) 21 The arrangement order of the SiO units is random.

[0270] In addition, as a divalent hydrocarbon group that may have an oxygen atom or a nitrogen atom, which connects the above-mentioned monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group to a silicon atom, the same group as the divalent linking group exemplified in component (B) above can be listed.

[0271] In addition, X' is a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group, specifically including groups represented by the following general formula.

[0272] [Chemistry 36]

[0273]

[0274] In the above formula, R 22 It is a divalent hydrocarbon group with 2 to 15 carbon atoms, specifically including ethylene, propyleneene, butylene, etc., with propyleneene being preferred.

[0275] Examples of cyclic organopolysiloxanes represented by the above general formula include the following compounds. It should be noted that in the following formula, Me represents a methyl group.

[0276] [Chemistry 37]

[0277]

[0278] (In the formula, t1”' is 2 or 3, and c1’ is an integer from 2 to 20.)

[0279] [Chemistry 38]

[0280]

[0281] (In the formula, V1”' is 2 or 3, and c1’ is an integer from 2 to 20.)

[0282] These (E) components can be used individually or in combination of two or more. In this case, the carboxylic anhydride that is solid at 23°C can be used in combination with the cyclic organopolysiloxane (fluorinated organopolysiloxane modified carboxylic anhydride compound).

[0283] Regarding the amount of component (E) mentioned above, it is 0.010 to 10 parts by weight, preferably 0.10 to 2 parts by weight, relative to 100 parts by weight of component (A). When it is 0.010 parts by weight or more, an effect sufficient to promote the adhesion of the composition of the present invention is obtained, and therefore it is preferred. On the other hand, when it is 10 parts by weight or less, the flowability of the composition of the present invention is improved, and the storage stability of the composition is also obtained, and therefore it is preferred.

[0284] [(F) Ingredients (Other Ingredients)]

[0285] In order to improve its practicality, in addition to the components (A) to (E) mentioned above, various compounding agents such as plasticizers, viscosity modifiers, flexibility enhancers, catalyst control agents for hydrogenation silylation reaction, inorganic fillers, adhesion promoters, adhesive additives other than component (D), and silane coupling agents may be added as needed. The amount of these additives mixed is arbitrary, as long as it does not impair the purpose of the invention and the properties of the composition and the physical properties of the cured product.

[0286] As plasticizers, viscosity modifiers, and flexibility enhancers, polyfluoromonoolefin compounds represented by the following general formula (55) and / or linear polyfluoro compounds represented by the following general formulas (56) and (57) can be used together. The number average molecular weight of these compounds is preferably 3,000 to 20,000.

[0287] Rf 4 -(X') p’ CH=CH2 (55)

[0288] In equation (57), X' and the above L 2 The Z (divalent linker) in the structure is the same, p' is 0 or 1, and Rf 4 It is a monovalent perfluoropolyether group represented by the following general formula.

[0289] [Chemistry 39]

[0290]

[0291] (In the formula, f' is an integer from 2 to 200, preferably an integer from 2 to 100, h' is an integer from 1 to 3, and the sum of f' and h' is greater than the Rf of the linear perfluoropolyether compound shown in the above general formula (1).) 1 The sum of p and q in the equation is small.

[0292] Y 5 -O-(CF2CF2CF2O) c2 -Y 5 (56)

[0293] [In the formula, Y] 5 Independently for the formula: C k’ F 2k’+1 -(k' is an integer from 1 to 3) represents the group, c2 is an integer from 1 to 200, and is greater than the Rf of the linear perfluoropolyether compound shown in the above general formula (1). 1 The z-value is small.

[0294] Y 6 -O-(CF2O) d2 (CF2CF2O) e2 -Y6 (57)

[0295] (where Y) 6 With the above Y 5 Similarly, d2 and e2 are each integers from 1 to 200, and the sum of d2 and e2 is greater than the Rf of the linear perfluoropolyether compound represented by the above general formula (1). 1 The sum of n and m in the above () is small. The repeating units in the above () can be arranged randomly.

[0296] Specific examples of polyfluoromonoalkenyl compounds represented by the above general formula (55) include the following substances. It should be noted that the following m' satisfies the above necessary conditions.

[0297] [Chemistry 40]

[0298]

[0299] As specific examples of linear polyfluorinated compounds represented by the above general formulas (56) and (57), the following substances can be listed for example. It should be noted that the following c2, d2, e2 and the sum of d2 and e2 satisfy the above necessary conditions.

[0300] CF3O-(CF2CF2CF2O) c2 -CF2CF3

[0301] CF3-(OCF2CF2) e2 (OCF2) d2 -O-CF3

[0302] Regarding the amount of polyfluorinated compounds in formulas (55), (56), and (57) above, it is 1 to 300 parts by mass relative to 100 parts by mass of component (A), preferably 50 to 250 parts by mass. Furthermore, a viscosity (at 23°C) in the range of 2000 to 50000 mPa·s is desirable.

[0303] In addition, as a control agent for the hydrosilylation reaction catalyst, examples include ethynylcyclohexanol (also known as 1-ethynyl-1-hydroxycyclohexane), 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, phenylbutynol, and other alkynols; reactants of chlorosilanes with the above-mentioned monovalent fluorinated substituents and alkynols; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, triallyl isocyanurate, etc.; or polyvinylsiloxanes, organophosphorus compounds, etc. By adding them, the curing reactivity and storage stability can be maintained to a certain extent.

[0304] As an inorganic filler, it can be added to reinforce or quasi-reinforcing fillers such as quartz powder, fused silica powder, diatomaceous earth, and calcium carbonate; inorganic pigments such as titanium dioxide, iron oxide, carbon black, and cobalt aluminate; heat-resistant improvers such as titanium dioxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate; thermally conductive agents such as alumina, boron nitride, silicon carbide, and metal powders; and conductive agents such as carbon black, silver powder, and conductive zinc white.

[0305] In addition, it is possible to add adhesive promoters such as carboxylic anhydrides and titanates, adhesive imparting agents other than component (D), and / or silane coupling agents.

[0306] [Method for manufacturing adhesive composition]

[0307] The adhesive composition of the present invention can be manufactured by uniformly mixing the above-mentioned components (A) to (D) and other optional components using a mixing device such as a planetary mixer, Ross mixer, or Hobart mixer, or a kneading device such as a kneader or a three-roller mixer as needed.

[0308] There are no particular limitations on the manufacturing method of the adhesive composition of the present invention; it can be manufactured by mixing the above-mentioned components. Alternatively, a two-component composition can be prepared and mixed before use.

[0309] The manufactured adhesive composition can also be cured at room temperature depending on the type of catalyst in component (C). Heating can be used to promote curing. In particular, in order to achieve good adhesion to various substrates, it is preferable to cure it at 60°C or higher, preferably 100 to 200°C, for a period of several minutes to several hours.

[0310] It should be noted that when using the adhesive composition of the present invention, the composition can be dissolved in a suitable fluorinated solvent, such as 1,3-bis(trifluoromethyl)benzene, FLUORINERT (manufactured by 3M), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, etc., at the desired concentration, depending on its use and purpose, within a range where there is no effect from venting during heat curing. In particular, the solvent is preferably used in film coating applications.

[0311] The adhesive composition of the present invention exhibits excellent adhesion to a wide range of substrates, including metals and plastics. Examples of such metals include aluminum, stainless steel (SUS), nickel, chromium, copper, zinc, and alloys of two or more of these. Examples of such plastics include epoxy resin, phenolic resin, PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PC (polycarbonate) resin, PPS (polyphenylene sulfide) resin, PA (polyamide) resin, PI (polyimide) resin, and LCP (liquid crystal polymer) resin. In this case, the thickness of the cured adhesive composition of the present invention is preferably about 80 μm to 1 mm.

[0312] Furthermore, the adhesive composition of the present invention is useful as an adhesive for various electrical and electronic components, etc. For example, it can be suitably used as an adhesive for inkjet printers, an adhesive for printheads, a sealant, a coating agent for rollers and belts of laser printers and copiers, an adhesive sealant and coating agent for various circuit boards, and a chip bonding material for automotive sensor manufacturing, etc. Specifically, for example, it is possible to manufacture a chip bonding material for automotive sensors containing the adhesive composition of the present invention, and also to manufacture a protective sealant or coating agent for printing and copying devices containing the adhesive composition of the present invention. If used, it is possible to manufacture automotive sensor articles in which a sensor chip is fixed by a cured product of the adhesive composition of the present invention, or to manufacture components for printing and copying devices in which a cured product of the adhesive composition of the present invention is used as a protective sealant or coating layer.

[0313] Example

[0314] Examples and comparative examples are shown below to specifically illustrate the present invention, but the present invention is not limited to the following examples. It should be noted that in the following examples, parts represent parts by mass. In addition, viscosity and adhesive strength are measured values ​​at 23°C (viscosity was determined according to the rotational viscosity method of viscosity test specified in JIS K6249, and adhesive strength was determined according to the tensile shear adhesive strength test method of adhesive-rigid bonded materials in JIS K6850). The number-average molecular weights of compounds (58), (64), and (65) were obtained as the number-average molecular weights converted from polystyrene in gel permeation chromatography (GPC) analysis using AK-225 (manufactured by Asahi Glass Co., Ltd.) as the elution solvent. In addition, the number-average molecular weights of compounds (59), (60), (61), (63), (66), and (67) were analyzed. 1 H-NMR determination and 19F-NMR measurements were performed based on the integral values ​​of each unit in the compound obtained from the obtained spectra. Regarding the vinyl content of component (A), for component (A1), infrared spectroscopy using a calibration curve was employed; for components (A2), (A3), and (A4), proton nuclear magnetic resonance spectroscopy using an internal standard was employed. 1 H-NMR) determination. Additionally, the Si-H basis content of components (B) ((B1), (B2), (B')) and components (D1), (D2)) was determined using proton nuclear magnetic resonance spectrometry with an internal standard. 1 Measured by H-NMR.

[0315] In addition, the mass reduction rate of each of the following compounds after heating at 150°C for 1 hour was determined using the following measurement method.

[0316] First, weigh the tare weight (W1) of the clean aluminum pan using a precision balance (read limit 0.0001 mg). Next, take a 1.5 g sample (compound) from the aluminum pan and weigh the pan containing the sample using the precision balance (W2). Then, place the aluminum pan containing the sample in a thermostat at 150°C for 1 hour. After heating, remove the aluminum pan from the thermostat and allow it to cool naturally in a desiccator. After natural cooling, weigh the aluminum pan containing the sample using the precision balance (W3). Calculate the mass reduction rate of the sample using the following formula.

[0317] {(W3-W1) / (W2-W1)}×100 (unit: %)

[0318] W1: Mass of aluminum disc (g)

[0319] W2: Mass of aluminum disc + mass of sample before heating (g)

[0320] W3: Mass of aluminum disc + mass of heated sample (g)

[0321] [Example 1]

[0322] To 100 parts of the polymer (A1) shown in formula (58) below (number average molecular weight 15550, mass reduction rate 0.5%, viscosity 10900 mPa·s, vinyl content 0.012 mol / 100 g), add 0.033 parts of an ethanol solution (C1) of platinum-divinyltetramethyldisiloxane complex (platinum concentration 3.0 wt%), 0.25 parts of a 60 wt% toluene solution of ethynylcyclohexanol, and (B1) the compound (B1) shown in formula (59) below (number average molecular weight 1... 906. 3.00 parts of (B2) compound (60) with a mass reduction rate of 7.0% and a Si-H base content of 0.16 mol / 100 g, 1.52 parts of (B2) compound (60) with a number-average molecular weight of 1720, a mass reduction rate of 16.0%, and a Si-H base content of 0.52 mol / 100 g), and 2.00 parts of (D1) compound (61) with a number-average molecular weight of 990 and a Si-H base content of 0.121 mol / 100 g) are mixed to prepare an adhesive composition. It should be noted that in the formula, Me represents methyl.

[0323] [Chemistry 41]

[0324]

[0325] (In the formula, m and n are integers greater than or equal to 1, and the average value of m + n is 90.)

[0326] [Chemistry 42]

[0327]

[0328] (In the formula, the average value of c' is 8.)

[0329] [Chemistry 43]

[0330]

[0331] (In the formula, the average value of i is 9.)

[0332] [Chemistry 44]

[0333]

[0334] (Contamination confirmation test during heat curing)

[0335] Next, in order to confirm whether ambient contamination caused by venting occurred during the heat curing of the composition, the following experiment was conducted.

[0336] Prepare four sensor chips and use a microscope to confirm that the gold pads on the sensor chips are not contaminated (before the test). Then, place the sensor chips in a clean glass dish, cover the dish, and place it in a thermostat at 150°C for 1 hour. After heating, remove the glass dish from the thermostat and allow it to cool naturally in a desiccator for 3 hours. Then, remove the sensor chips from the glass dish and, as before placing them in the thermostat, use a microscope to confirm that the gold pads are not contaminated.

[0337] Next, in a clean glass dish, 10g of the adhesive composition from Example 1 and four sensor chips were placed adjacent to each other. After heating (placed in a thermostat at 150°C for 1 hour) and naturally cooling (naturally cooled in a desiccator for 3 hours) as described above, the sensor chips were removed after the test, and the contamination of the gold pads was examined using a microscope. The results are shown in Table 1.

[0338] In cases where exhaust gases generated during the heat curing of the adhesive composition contaminate the sensor chip, it was confirmed that the adhesion of the exhaust components caused visual defects (discoloration). Therefore, if the appearance of the sensor chip is approximately the same as that of the blank sample, it can be said that no contamination caused by exhaust gases during the heat curing of the composition has occurred.

[0339] [Example 2]

[0340] Except that, in Example 1, 0.2 parts of the compound shown in Formula (62) below (E1) were added to 100 parts of the polymer shown in Formula (58) above (A1), the adhesive composition was prepared in the same manner as in Example 1. Contamination confirmation tests and evaluations during heat curing were performed on this adhesive composition in the same manner as in Example 1. The results are shown in Table 1.

[0341] [Chemistry 45]

[0342]

[0343] [Example 3]

[0344] 100 parts of the polymer shown in formula (58) above (A1) and 6.3 parts of fumed silica (Aerosil R-972 (trade name manufactured by Aerosil Corporation)) were mixed in a planetary mixer at room temperature for 30 minutes, and then mixed at 150°C for 1 hour under reduced pressure of -98.0 kPaG. After cooling the mixture to room temperature, 0.033 parts of an ethanol solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 3.0% by mass), 0.25 parts of a 60% by mass toluene solution of ethynylcyclohexanol, 3.00 parts of the compound shown in formula (59) above (B1), 1.52 parts of the compound shown in formula (60) above (B2), 2.00 parts of the compound shown in formula (61) above (D1), and 0.2 parts of the compound shown in formula (62) above were added and mixed to prepare an adhesive composition. For this adhesive composition, the same contamination confirmation test and evaluation during heat curing as in Example 1 were performed. The results are shown in Table 1.

[0345] [Example 4]

[0346] In Example 3, 0.20 parts of the compound shown in Formula (58) below (D2) (number-average molecular weight 1024, Si-H group content 0.098 mol / 100g) were added to 100 parts of the polymer shown in Formula (58) above (A1). Otherwise, the adhesive composition was prepared using the same method as in Example 3. Contamination confirmation tests and evaluations during heat curing were performed on this adhesive composition, as in Example 1. The results are shown in Table 1. It should be noted that in the formula, Me represents methyl.

[0347] [Chemistry 46]

[0348]

[0349] [Example 5]

[0350] An adhesive composition was prepared by mixing 100 parts of the polymer (number average molecular weight 6450, mass reduction rate 0.4%, viscosity 60 mPa·s, vinyl content 0.031 mol / 100 g) shown in formula (64) below (A2), 0.033 parts of an ethanol solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 3.0 wt%), 0.25 parts of a 60 wt% toluene solution of ethynylcyclohexanol, 19.4 parts of the compound shown in formula (59) above (B1), 1.79 parts of the compound shown in formula (60) above (B2), 2.0 parts of the compound shown in formula (61) above (D1), and 0.2 parts of the compound shown in formula (62) above (E1). The adhesive composition was subjected to the same heat curing contamination confirmation test and evaluation as in Example 1. The results are shown in Table 1.

[0351] [Chemistry 47]

[0352] (A2)

[0353] CH2=CH-CH Z -O-CH2-CF2-(OC2F4) n -(OCF2) m -O-CF2-CH2-O-CH2-CH=CH2 (6a)

[0354] (In the formula, m and n are integers greater than or equal to 1, and the average value of m+n is 34.)

[0355] [Example 6]

[0356] In Example 3, 100 parts of the polymer shown in Formula (58) below (A3) (number-average molecular weight 15630, mass reduction rate 0.4%, viscosity 11000 mPa·s, vinyl content 0.012 mol / 100 g) were used instead of the polymer shown in Formula (58) above (A1), and the adhesive composition was prepared in the same manner as in Example 3. The same heat curing contamination confirmation test and evaluation were performed on this adhesive composition as in Example 1. The results are shown in Table 1. It should be noted that in the formula, Me represents methyl.

[0357] [Chemistry 48]

[0358]

[0359] (In the formula, m and n are integers greater than or equal to 1, and the average value of m + n is 90.)

[0360] [Comparative Example 1]

[0361] In Example 1, instead of the compound shown in formula (59) above (B1), 1.83 parts of the compound shown in formula (66) below (number-average molecular weight 762, mass reduction rate 100%, Si-H base content 0.394 mol / 100 g) were used, and the compound shown in formula (60) above (B2) was replaced with 1.18 parts. Otherwise, the adhesive composition was prepared in the same manner as in Example 1. Contamination confirmation tests and evaluations during heat curing were performed on this adhesive composition in the same manner as in Example 1. The results are shown in Table 1. It should be noted that in the formula, Me represents methyl.

[0362] [Chemistry 49]

[0363]

[0364] [Comparative Example 2]

[0365] Except that, in Example 1, instead of 100 parts of the polymer (A1) shown in Formula (58) below (67) (number-average molecular weight 1810, mass reduction rate 28%, viscosity 28 mPa·s, vinyl content 0.10 mol / 100 g), 100 parts of the polymer (A1) shown in Formula (58) were used, the adhesive composition was prepared in the same manner as in Example 1. The same contamination confirmation test and evaluation during heat curing were performed on this adhesive composition as in Example 1.

[0366] [Transformation 50]

[0367] (A4)

[0368] CH2=CH-CH2-O-CH2-CF2-(OC2F4) n -(OCF2) m -O-CF2-CH2-O-CH2-CH=CH2 (67)

[0369] (In the formula, m and n are integers greater than or equal to 1, and the average value of m + n is 9.)

[0370] [Table 1]

[0371] Example 1 none Example 2 none Example 3 none Example 4 none Example 5 none Example 6 none Comparative Example 1 have Comparative Example 2 have

[0372] The appearance photographs of the sensor chip before and after the contamination confirmation test during heat curing in Example 1 are shown below. Figure 1 . Figure 1 The circular pattern in the center of the photo represents the gold pads of the sensor chip. In Example 1, the sensor chip (in its pre-test (blank) state) is compared to... Figure 1 Compared to (a)), the sensor chip after the experiment ( Figure 1 (b) No appearance defects, primarily discoloration, were found. Furthermore, for Examples 2-6, similar to Example 1, no contamination (discoloration caused by liquid or oily impurities adhering to the gold pads) was confirmed on the gold pads. On the other hand, photographs of the sensor chip's appearance before and after the contamination confirmation test during heat curing in Comparative Example 1 are shown below. Figure 2 In Comparative Example 1, the sensor chip (in its pre-experiment (blank) state) was compared with that in the experimental state. Figure 2 Compared to (a), it was confirmed that the sensor chip after the test ( Figure 2 (b) Discoloration due to the adhesion of liquid or oily impurities. Similarly to Comparative Example 1, gold pad contamination of the sensor chip was confirmed in Comparative Example 2.

[0373] (Adhesion test)

[0374] Two 100mm × 25mm test panels of various adherends (aluminum (Al), stainless steel (SUS), polybutylene terephthalate (PBT), and polyphenylene sulfide (PPS)) listed in Table 2 were overlapped by 10mm at each end, sandwiching a 1mm thick layer of the compositions obtained in Examples 1-6 and Comparative Examples 1 and 2. The panels were then heated at 150°C for 1 hour to cure the compositions and produce bonding test pieces. Tensile shear bonding tests (tensile speed 50mm / min) were then performed on these test pieces to evaluate the bond strength (shear bond strength) and agglomeration failure rate. The results are shown in Table 2. In the table, the values ​​in the upper section represent the shear bond strength, and the values ​​in parentheses in the lower section represent the agglomeration failure rate (%).

[0375] [Table 2]

[0376]

Claims

1. An adhesive composition comprising: (A) A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a number-average molecular weight of 2000 or more: 100 parts by mass of (A) when (A) is heated alone at 150°C for 1 hour, the mass reduction rate of (A) is less than 1%. (B) A fluorinated organohydrogen polysiloxane compound having two or more hydrogen atoms bonded to silicon atoms in one molecule, and having one or more fluorinated organic groups, without epoxy groups or trialkoxysilyl groups, having a number average molecular weight of 1000 or more and 4000 or less, and having a cyclic siloxane skeleton, wherein the mass reduction rate of component (B) when heated alone at 150°C for 1 hour is less than 20%; the amount is such that relative to 1 mole of alkenyl group in component (A), the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 2.5 moles. (C) Platinum group metal compounds: 0.1–1000 ppm relative to the mass of component (A), expressed in platinum group metal atomic conversions. (D) An organohydrogen polysiloxane compound having one or more hydrogen atoms bonded to silicon atoms in one molecule, and epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms, with a number average molecular weight of 700 or more and less than 2000: in such amounts that, relative to 1 mole of alkenyl groups in component (A), the number of hydrogen atoms bonded to silicon atoms in component (D) is 0.005 to 1.5 moles.

2. The adhesive composition according to claim 1, wherein, (A) The component is a linear perfluoropolyether compound represented by the following general formula (1). [Chemistry 1] In the formula, A 1 Each is independently selected from any one of the following groups: a divalent organic group with 1 to 4 carbon atoms that may contain ether or amide bonds; a group represented by the following general formula (2); and a group represented by the following general formula (3). [Chemistry 2] In the formula, Y 1 Y is a hydrogen atom, methyl, ethyl, or phenyl. 2 It is a hydrogen atom, methyl, ethyl, or trifluoromethyl, and o is an integer from 1 to 6, wherein the bonding end with * indicates a bond with Rf. 1 bonding, B is a carbon atom or a silicon atom, X 1 Each is independent, at least two are alkenyl groups, and the others are X groups. 1 When B is a carbon atom, it is either a hydrogen atom or a methyl atom; when B is a silicon atom, it is a methyl atom. Rf 1 It is a divalent perfluoropolyether group.

3. The adhesive composition according to claim 1, wherein, When component (A) is heated alone at 150°C for 1 hour, the mass reduction rate of component (A) is less than 0.5%.

4. The adhesive composition according to claim 1, wherein, (A) The alkenyl content of component A is 0.002 to 0.3 mol / 100g.

5. The adhesive composition according to claim 1, wherein, (B) The component is a fluorinated organohydrogen polysiloxane compound represented by the following general formula (4). [Chemistry 3] In the formula, R 1 For unsubstituted or halogenated monovalent hydrocarbon groups, L 1 The following general formula (5) represents a monovalent fluorinated organic group containing a monovalent perfluoropolyether group, which can be bonded to silicon atoms via a divalent linking group. w1 is an integer from 0 to 50, x1 is an integer from 2 to 50, y1 is an integer from 1 to 50, w1+x1+y1 is an integer satisfying a number average molecular weight of 1000 to 4000, and the repeating units of ( ) can be arranged randomly. E-(C4F8O) c -(C3F6O) d -(C2F4O) e -(CF2O) f -C g F 2g - (5) E is a perfluoroalkyl group with 1 to 6 carbon atoms or fluorine atoms, c, d, e, and f are each independent integers from 0 to 20, with 2 ≤ c + d + e + f ≤ 20, g is an integer from 1 to 3, and the repeating units of the above ( ) can be arranged randomly.

6. The adhesive composition according to claim 1, wherein, (D) The component has one or more monovalent perfluoroalkyl or monovalent perfluorooxyalkyl groups bonded to silicon atoms via a divalent linking group selected from nitrogen, carbon and oxygen atoms in one molecule.

7. The adhesive composition according to claim 1, wherein, Relative to 100 parts by mass of component (A), it also contains 0.010 to 10 parts by mass of carboxylic anhydride (E).

8. The adhesive composition according to claim 1, wherein, (D) The component is any one of the substances represented by the following general formula. In the formula, R 2 For unsubstituted or halogenated monovalent hydrocarbon groups, L 2 M is a monovalent perfluoropolyether group bonded to silicon atoms via a divalent linking group, M is an epoxy or trialkoxysilyl group bonded to silicon atoms via a carbon atom or carbon and oxygen atoms, w2 is an integer satisfying 0≤w2≤50, x2 is an integer satisfying 1≤x2≤50, y2 is an integer satisfying 0≤y2≤50, z2 is an integer satisfying 1≤z2≤50, and w2+x2+y2+z2 is an integer satisfying a number average molecular weight of 700 to 2000. The repeating units of the above ( ) can be arranged randomly.

9. The adhesive composition according to claim 1, wherein, (D) The component has epoxy groups, represented by the following formula, bonded to silicon atoms via carbon atoms or carbon and oxygen atoms. ， In the formula, R 3 It is a divalent hydrocarbon group with 1 to 10 carbon atoms that can be sandwiched with oxygen atoms.

10. The adhesive composition according to claim 1, wherein, (A) The number average molecular weight of the component is above 1000 and below 2500.

11. The adhesive composition according to claim 1, further comprising, in a proportion of the same mass as component (B), a fluorinated organohydrogen polysiloxane compound having two or more hydrogen atoms bonded to silicon atoms in one molecule, and having one or more fluorinated organic groups, free of epoxy and trialkoxysilyl groups, having a number average molecular weight of 1000 or more and 4000 or less, having a linear siloxane backbone, wherein the mass reduction rate of the compound when heated alone at 150°C for 1 hour is greater than 15% and less than 20%.

12. A chip bonding material comprising an adhesive composition according to any one of claims 1 to 11.

13. The chip bonding material according to claim 12, used in an automotive sensor.

14. A protective sealant or coating agent comprising an adhesive composition according to any one of claims 1 to 11.

15. The protective sealant or coating agent according to claim 14, used in printing, copying apparatus or fuel cell.

16. An electrical-electronic component having a cured form of the adhesive composition according to any one of claims 1 to 11.

17. The electrical-electronic component according to claim 16, which is an article for an automotive sensor in which a sensor chip is fixed by a cured adhesive composition.

18. The electrical-electronic component according to claim 16, which is a component for a printing or copying apparatus or a fuel cell, wherein the cured adhesive composition is used as a protective seal or coating layer.

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