Electric / electronic component

Abstract

To provide an electric / electronic component having a fluorine-containing elastomer cured product with little contamination of surrounding components due to outgas during heat curing.SOLUTION: (A) an alkenyl group-containing linear perfluoropolyether compound having a number-average molecular weight of at least 2000, (B) a crosslinker consisting of (B1) and (B2), (B1) a fluorine-containing cyclic organohydrogenpolysiloxane compound free of epoxy and trialkoxysilyl groups and having a number-average molecular weight of 1,000 to 4000, (B2) a fluorine-containing cyclic organohydrogenpolysiloxane compound free of epoxy and trialkoxysilyl groups and having a number-average molecular weight of 1,000 to 3,000, An electrical or electronic component comprising a cured product of an adhesive composition comprising an organohydrogensiloxane compound having a weight loss of more than 15% when heated at 150 °C for 1 hour, (C) a platinum group metal compound, and (D) an organohydrogenpolysiloxane compound having an epoxy group and / or trialkoxysilyl group bonded to a silicon atom through a carbon atom or a carbon atom and an oxygen atom and having a number average molecular weight of 700 to 4,000.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to electrical and electronic components having a cured product of a perfluoropolyether adhesive composition that causes minimal contamination of surrounding components due to outgassing during heat curing, firmly bonds to various substrates such as metals and plastics, and gives, after curing, a fluorine-containing elastomer cured product that has excellent solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, electrical properties, etc. [Background technology]

[0002] Curable fluorine-containing elastomer compositions utilizing the addition reaction of alkenyl groups and hydrosilyl groups are known, and a composition has been proposed in which self-adhesive properties have been imparted by adding an organopolysiloxane having hydrosilyl groups and epoxy groups and / or trialkoxysilyl groups as a third component (adhesion improver) to the composition (Patent Document 1: JP-A-9-95615). The composition can be cured by heating for a short period of time, and the resulting cured product (cured fluorine-containing elastomer product) has excellent solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, electrical properties, etc., and is therefore used for adhesive applications in various industrial fields where these properties are required.

[0003] However, it has been pointed out that gaseous impurities (commonly referred to as "outgassing") are generated during the heat curing of this composition, contaminating surrounding components and causing problems. For example, when this composition is used as a sealant for the head of an inkjet printer, the outgassing (gaseous fluorine-containing low-molecular-weight compounds) generated during the heat curing process contaminates the ink ejection path and the vicinity of the ejection port, resulting in problems such as changes in ink ejection properties. In the manufacturing process of automotive sensors, when this composition is used as a material (die attach material) for attaching chips to resin substrates, the outgassing contaminates the gold pads on the chip, preventing wire bonding. This outgassing is thought to be generated by the evaporation of low-molecular-weight components, such as the perfluoropolyether compound with a low degree of polymerization in the base polymer and the fluorine-containing organohydrogensiloxane crosslinker, as well as fluorine-containing organic compounds or non-fluorine-based organic compounds blended as adhesion promoters, from the composition before the curing reaction is completed. As a means for suppressing contamination of surrounding parts due to outgassing, it is known to use an adhesive composition in which the molecular weight of a fluorine-containing organic compound or a non-fluorine-based organic compound used as a component of an adhesion improver is 2,000 or more, and the volatile content at 105°C is very low (Patent Document 2: Japanese Patent No. 4582287). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-95615 [Patent Document 2] Patent No. 4582287 Summary of the Invention [Problem to be solved by the invention]

[0005] Using a perfluoropolyether adhesive composition made solely from components with a molecular weight of 2,000 or greater reduces outgassing, while the viscosity of high-molecular-weight components other than the base polymer is more likely to affect the overall viscosity of the adhesive composition. For example, blending a high-molecular-weight fluorine-containing component with a lower viscosity than the base polymer (alkenyl group-containing perfluoropolyether compound) tends to result in a low-viscosity perfluoropolyether adhesive composition. Blending a high-molecular-weight fluorine-containing component with a higher viscosity than the base polymer also tends to result in a high-viscosity perfluoropolyether adhesive composition. Furthermore, the cured fluorine-containing elastomer obtained by curing a perfluoropolyether adhesive composition containing a high-molecular-weight fluorine-containing component other than the base polymer tends to be soft (low hardness). In die-attach applications, perfluoropolyether adhesive compositions are used to secure sensor chips to substrates. However, if the cured fluorine-containing elastomer obtained from the perfluoropolyether adhesive composition is soft, the flexibility of the cured fluorine-containing elastomer may prevent the chip from being firmly attached, making wire bonding difficult. The addition of an inorganic filler can increase the viscosity of the perfluoropolyether adhesive composition and improve the physical properties of the cured fluorine-containing elastomer, but may make it difficult to achieve adhesion to metals, resins, etc. For the above reasons, it is preferable that some or all of the components other than the base polymer in the perfluoropolyether adhesive composition have relatively low molecular weights, and there is a demand for a perfluoropolyether adhesive composition that causes little contamination of surrounding parts due to outgassing during curing.

[0006] The present invention has been made in consideration of the above circumstances, and has as its object the provision of an electrical / electronic component having a cured product of a perfluoropolyether adhesive composition which is less likely to contaminate surrounding components due to outgassing during heat curing, which firmly bonds to various substrates such as metals and plastics, and which, after curing, gives a fluorine-containing elastomer cured product which is excellent in solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, electrical properties, etc. [Means for solving the problem]

[0007] As a result of extensive research conducted by the present inventors to solve the above problems, they discovered that by combining a base polymer with a number average molecular weight of 2,000 or more and low in low molecular weight components that cause outgassing with a crosslinking agent with a number average molecular weight of 1,000 to 4,000, it is possible to obtain a perfluoropolyether adhesive composition that causes almost no contamination of surrounding parts due to outgassing during heat curing, even if the number average molecular weight of the adhesion improver, a fluorine-containing organic compound or a non-fluorine-based organic compound, is not 2,000 or more (specifically, even if the adhesion improver is a relatively low molecular weight component of around 700 to 2,000), thereby completing the present invention.

[0008] Accordingly, the present invention provides the following electric and electronic components: 1. (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and having a number average molecular weight of 2,000 or more; (B) a crosslinker component consisting of the following (B1) and (B2): (B1) A fluorine-containing organohydrogenpolysiloxane compound having a cyclic siloxane skeleton, which has two or more hydrogen atoms bonded to silicon atoms in one molecule, has one or more fluorine-containing organic groups, does not contain epoxy groups or trialkoxysilyl groups, and has a number average molecular weight of 1,000 or more and 4,000 or less; (B2) an organohydrogensiloxane compound that does not contain an epoxy group or a trialkoxysilyl group and that exhibits a mass loss rate of more than 15% when heated at 150°C for 1 hour; (C) platinum group metal compounds, and (D) An organohydrogenpolysiloxane compound having, in one molecule, at least one hydrogen atom bonded to a silicon atom and at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and having a number average molecular weight of 700 to 4,000. An electrical or electronic component having a cured product of an adhesive composition containing the adhesive. 2. 2. The electrical / electronic part according to 1, wherein the adhesive composition contains the component (B2) in an amount equal to or less than the amount of the component (B1) by mass. 3. 3. The electric or electronic part according to 1 or 2, wherein the organohydrogensiloxane compound of component (B2) is a fluorine-containing organohydrogensiloxane compound. 4. 4. The electric or electronic part according to any one of 1 to 3, wherein the fluorine-containing organohydrogenpolysiloxane compound of component (B1) loses mass by 15% or less when heated at 150° C. for 1 hour. 5. 5. The electric potential component according to any one of 1 to 4, wherein the number average molecular weight of the compound of component (B) is smaller than the number average molecular weight of the linear perfluoropolyether compound of component (A). 6. 6. The electric / electronic part according to any one of 1 to 5, wherein the linear perfluoropolyether compound of component (A) has a number average molecular weight of more than 4,000. 7. 7. The electric or electronic component according to any one of 1 to 6, wherein the amount of component (B) blended is such that the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 2.5 moles per mole of alkenyl groups in component (A). 8. 8. The electric or electronic component according to any one of 1 to 7, wherein the amount of component (D) blended is such that the number of hydrogen atoms bonded to silicon atoms in component (D) is 0.005 to 1.5 moles per mole of alkenyl groups in component (A). 9. 9. An electrical or electronic component according to any one of 1 to 8, characterized in that the adhesive composition is subjected to the following contamination confirmation test during heat curing, and no contamination of the gold pads on the sensor chip is confirmed by microscopic observation after the test. (Contamination confirmation test during heat curing) Prepare four sensor chips and use a microscope to confirm that the gold pads on the sensor chips are not contaminated. Then, place the sensor chips in a clean glass dish, cover the glass dish, and leave it in an incubator at 150°C for one hour. After this heating, remove the glass dish from the incubator and allow it to cool in a desiccator for three hours. Then, remove the sensor chips from the glass dish and use a microscope to confirm that the gold pads are not contaminated, just as they were before leaving them in the incubator. Next, 10 g of the sealant and four sensor chips are placed adjacent to each other in a clean glass petri dish, and heated (left in a 150°C incubator for 1 hour) and allowed to cool (allowed to cool in a desiccator for 3 hours) according to the method described above. After this test, the sensor chips are removed and the degree of contamination of the gold pads is checked under a microscope. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide electrical and electronic components which have a cured product that causes very little contamination of surrounding components due to outgassing during heat curing, adheres firmly to various substrates such as metals and plastics, and has excellent solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, electrical properties, etc. after curing. [Brief explanation of the drawings]

[0010] [Figure 1] 1A and 1B are diagrams showing the appearance of a sensor chip in a test to check for contamination during heat curing in Example 1, where (a) is a photograph of the appearance before the test to check for contamination during heat curing, and (b) is a photograph of the appearance after the test to check for contamination during heat curing. [Figure 2] 1A and 1B are diagrams showing the appearance of the sensor chip in the test for checking contamination during heat curing in Comparative Example 1, where (a) is a photograph of the appearance before the test for checking contamination during heat curing, and (b) is a photograph of the appearance after the test for checking contamination during heat curing. BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The present invention will be described in further detail below. [Adhesive composition] The adhesive composition according to the present invention is characterized by containing the following components (A), (B), (C) and (D):

[0012] [Component (A)] The linear perfluoropolyether compound of component (A) used in the adhesive composition of the present invention has at least two alkenyl groups in each molecule and a number average molecular weight of 2,000 or more, and when component (A) is heated alone at 150°C for 1 hour, the mass loss of component (A) is 1% or less. Preferably, as represented by general formula (1) described below, the linear perfluoropolyether compound has a divalent perfluoroalkyl ether structure in the main chain, and acts as the main agent (base polymer) in the adhesive composition of the present invention.

[0013] In the present invention, the degree of polymerization (or molecular weight) of the linear polyfluoro compound, which reflects the number of repetitions of the perfluorooxyalkylene units constituting the main chain perfluoropolyether structure, can be determined, for example, as the polystyrene-equivalent number-average degree of polymerization (or number-average molecular weight) in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. The number-average degree of polymerization (or number-average molecular weight) of the linear polyfluoro compound is 19 It can also be calculated from F-NMR. The component (A) is preferably a compound having a number-average molecular weight of 2,000 or more, particularly 4,000 or more, obtained by the synthesis method described in JP-A-9-95615. Linear perfluoropolyether compounds with a number-average molecular weight of less than 2,000 are undesirable because they tend to volatilize as outgassing during heat curing, causing contamination of surrounding components. The upper limit of the number-average molecular weight should be 50,000 or less, particularly 20,000 or less.

[0014] Furthermore, the linear perfluoropolyether compound of component (A) has a mass loss rate of 1% or less when heated alone at 150°C for 1 hour (150°C heat treatment), and preferably a mass loss rate of 0.5% or less. If the mass loss rate of the linear perfluoropolyether compound (A) due to this heat treatment at 150°C is greater than 1% (particularly 1.0%), outgassing will occur from the adhesive composition containing this compound during heat curing, causing contamination.

[0015] The mass loss rate can be determined using the following measurement method. The tare weight (W1) of a clean aluminum dish is weighed using a precision balance (reading limit 0.0001 mg). Next, a sample is placed on the aluminum dish, and the mass (W2) of the aluminum dish with the sample on it is weighed using the precision balance. The aluminum dish with the sample on it is left in an incubator (in air) at 150°C for one hour. After heating, the aluminum dish is removed from the incubator and allowed to cool in a desiccator. After cooling, the mass (W3) of the aluminum dish with the sample on it is weighed using the precision balance. The mass loss rate of this sample is determined using the formula below. {(W3-W1) / (W2-W1)} x 100 (unit: %) W1: Mass of aluminum dish (g) W2: Mass of aluminum dish + mass of sample before heating (g) W3: Mass of aluminum dish + mass of sample after heating (g) The method for measuring the mass loss rate is the same for components (B) and (D) described below.

[0016] In addition, the linear perfluoropolyether compound represented by the general formula (1) described below may inevitably contain components with a number average molecular weight of less than 2,000 among the perfluoropolyether compounds with a low degree of polymerization, which may cause outgassing.

[0017] Therefore, the component (A) from which low-molecular-weight components have been removed may be prepared by, for example, subjecting the linear perfluoropolyether compound represented by the general formula (1) described below to the following operation 1 as a pretreatment.

[0018] [Operation 1] The linear perfluoropolyether compound, preferably a linear perfluoropolyether compound represented by the general formula (1) described later, is subjected to reduced pressure treatment at a pressure of 1,330 Pa or less, preferably 665 Pa or less, at a temperature of 100 to 300°C, preferably 150 to 250°C, for 1 hour or more, preferably 5 hours or more.

[0019] Component (A) is preferably a linear perfluoropolyether compound having a structure represented by the following general formula (1): In the present invention, "linear" means that perfluorooxyalkylene units, which are repeating units constituting the main chain perfluoropolyether structure, are bonded (linked) to each other in a linear chain, and each perfluorooxyalkylene unit itself may have a branched structure, such as an [OCF2CF(CF3)] unit. [ka] [In the formula, A 1 are each independently any group selected from a divalent organic group having 1 to 4 carbon atoms which may contain an ether bond or an amide bond, a group represented by the following general formula (2) and a group represented by the following general formula (3), [ka] (In the formula, Y 1 is a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and Y 2 is a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group, and o is an integer of 1 to 6. The bond marked with an asterisk (*) is Rf 1 ) B is a carbon atom or a silicon atom, and X 1 are independent and there are six X's in the molecule (three at each end of the molecular chain). 1 At least two of the X are alkenyl groups, and the other X 1 is a hydrogen atom (only when B is a carbon atom) or a methyl group, and Rf 1is a divalent perfluoropolyether group.

[0020] In the above general formula (1), A 1 is any group selected from a divalent organic group having 1 to 4 carbon atoms which may contain an ether bond or an amide bond, a group represented by the following general formula (2) and a group represented by the following general formula (3): [ka] (In the formula, Y 1 is a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and Y 2 is a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group, and o is an integer of 1 to 6. The bond marked with an asterisk (*) is Rf 1 (The same applies below.)

[0021] A 1 Examples of the alkyl group include -CH2-*, -OCH2-*, -CH2CHOCH2-*, -CH2-NH-CO-*, -CH2CH2-NH-CO-*, -CH2-NCH3-CO-*, and groups represented by the following general formulae (2A), (2B), (2C), (3A), (3B) and (3C), with the group represented by general formula (2A) or (3A) being preferred. In the formulae, Me is a methyl group and Et is an ethyl group. [ka]

[0022] In the above general formula (1), B is a carbon atom or a silicon atom. In addition, there are six X in the molecule (i.e., three at each end of the molecular chain). 1 At least two of these (especially three at each end of the molecular chain) are present. 1 At least one of X is an alkenyl group, preferably one having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and having a CH2=CH- structure at the terminal. Examples include vinyl, allyl, propenyl, isopropenyl, butenyl, and hexenyl groups, with vinyl and allyl being preferred.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 becomes a methyl group when B is a silicon atom.

[0023] In the above general formula (1), Rf 1 is a divalent perfluoropolyether group, -C a F 2a It contains a repeating unit of O- (wherein a is an integer of 1 to 6), and examples thereof include those represented by the following formula (6). -(C a F 2a O) x - (6) (In formula (6), a is an integer of 1 to 6, and x is an integer of 5 to 600, preferably an integer of 10 to 400, and more preferably an integer of 30 to 200.)

[0024] Above formula-C a F 2a Examples of the repeating unit represented by O- include units represented by the following formulas. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O-

[0025] Among these, the units represented by the following formula are particularly preferred. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O-

[0026] The repeating unit in the divalent perfluoropolyether group may be composed of one of these alone or a combination of two or more of them.

[0027] The divalent perfluoropolyether group preferably contains a structure represented by any one of the following formulas (7) to (11). [ka] (wherein D is a fluorine atom or a trifluoromethyl group; p, q, and r are integers satisfying p≧0, q≧0, 0≦p+q≦200, particularly 2≦p+q≦150, and 0≦r≦6 (when p+q=0, 1≦r≦6); 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, particularly 2≦s+t≦150, 0 ≦u≦4, 2≦s+t+u≦150, v and w are integers that satisfy 1≦v≦100, 1≦w≦100, 2≦v+w≦150, respectively, z is an integer that satisfies 1≦z≦200, k', a'' and a''' are integers that satisfy 1≦k'≦3, 1≦a''≦6, 1≦a'''≦6, a''≠a''', respectively, and z' is an integer that satisfies 1≦z'≦200. The repeating units in ( ) of formula (9) may be arranged randomly.

[0028] In the above general formula (1), Rf 1 Specific examples of the compound include those represented by the following formulas (12) to (21). [ka] (In the above formula (12), p, q, and r are integers that satisfy p≧0, q≧0, 0≦p+q≦200, particularly 2≦p+q≦150, and 0≦r≦6, respectively. In the above formulas (13), (14), (15), (17), and (18), n is an integer of 1 to 100, m is an integer of 1 to 100, and n+m is an integer of 2 to 200. In the above formula (16), n1 is an integer of 2 to 200. In the above formula (19), z is an integer of 1 to 200. In the formula (20), n2 is an integer of 2 to 200. In the formula (21), z' is an integer of 1 to 200. The repeating units in parentheses in the formulas (17) and (18) may be arranged randomly.)

[0029] When B is a silicon atom, the component (A) represented by the above general formula (1) is particularly preferably one represented by the following formulas (22) to (35), where Me is a methyl group and Et is an ethyl group.

[0030] [ka] (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.)

[0031] [ka] (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.)

[0032] [ka] (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.)

[0033] [ka] (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.)

[0034] [ka] (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.)

[0035] When B is a carbon atom, the component (A) represented by the above general formula (1) is preferably one represented by the following formula: [ka] (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.)

[0036] The alkenyl group content in the linear perfluoropolyether compound of formula (1) is preferably 0.002 to 0.3 mol / 100 g, and more preferably 0.008 to 0.12 mol / 100 g. If the alkenyl group content in the linear perfluoropolyether compound is less than 0.002 mol / 100 g, the degree of crosslinking may be insufficient, which is undesirable, and if the alkenyl group content exceeds 0.3 mol / 100 g, the mechanical properties of the cured product as a rubber elastomer may be impaired, which is undesirable.

[0037] The viscosity (23°C) of the linear perfluoropolyether compound of component (A) is preferably in the range of 40 to 100,000 mPa·s, more preferably 50 to 50,000 mPa·s, and even more preferably 60 to 20,000 mPa·s, because the cured product of the composition of the present invention has suitable physical properties when used for sealing, potting, coating, impregnation, etc. Within this viscosity range, the most appropriate viscosity can be selected depending on the application. In the present invention, the viscosity (23°C) can be measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.) (the same applies in the examples).

[0038] As the component (A), these linear perfluoropolyether compounds can be used either individually or in combination of two or more.

[0039] [(B) Component] Component (B) used in the adhesive composition of the present invention is a fluorine-containing organohydrogenpolysiloxane compound that has two or more silicon-bonded hydrogen atoms (Si-H groups) per molecule, has one or more fluorine-containing organic groups, is free of epoxy groups and trialkoxysilyl groups, has a number-average molecular weight of 1,000 or more and 4,000 or less, and when heated alone at 150°C for 1 hour, the mass loss of component (B) is 20% or less, and functions as a crosslinker or chain extender for component (A).

[0040] The number-average molecular weight of component (B) is 1,000 to 4,000, preferably 1,000 to 2,500. Fluorine-containing organohydrogenpolysiloxane compounds with a number-average molecular weight of less than 1,000 are undesirable because, when present in the adhesive composition, they volatilize as outgassing during heat curing, causing contamination. On the other hand, fluorine-containing organohydrogenpolysiloxane compounds with a number-average molecular weight of more than 4,000 are undesirable because their inherent viscosity is likely to be reflected in the adhesive composition, making it difficult to maintain the viscosity of the adhesive composition within a specific range.

[0041] Furthermore, the fluorine-containing organohydrogenpolysiloxane compound of component (B) has a mass loss of 20% or less when heated alone at 150°C for 1 hour (150°C heat treatment), and this mass loss is preferably 15% or less, and more preferably 8% or less. If the mass loss of the fluorine-containing organohydrogenpolysiloxane compound exceeds 20%, outgassing may occur from the adhesive composition containing it during heat curing, which may cause contamination of surrounding parts, which is undesirable.

[0042] Furthermore, the adhesive composition of the present invention must have a mass loss of 1% or less (particularly 1.0%) when component (A) is heated alone at 150°C for 1 hour, and a mass loss of 20% or less when component (B) is heated alone at 150°C for 1 hour. This suppresses outgassing during heat curing of the adhesive composition of the present invention, making it possible to prevent contamination.

[0043] Furthermore, in terms of compatibility with component (A), dispersibility, uniformity after curing, and the like, it is more preferable that the fluorine-containing organic group in the molecule of component (B) has one or more perfluoroalkyl groups, perfluorooxyalkyl groups (monovalent perfluoropolyether groups), perfluoroalkylene groups, or perfluorooxyalkylene groups (divalent perfluoropolyether groups) in one molecule.

[0044] In particular, the component (B) preferably has a monovalent perfluoropolyether group represented by the following general formula (5). E-(C4F8O) c -(C3F6O) d -(C2F4O) e -(CF2O) f -C g F 2g - (5) (E is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms; c, d, e, and f each independently represent an integer of 0 to 20, and 2≦c+d+e+f≦20; and g is an integer of 1 to 3. The repeating units in the above ( ) may be arranged randomly.)

[0045] In the above general formula (5), if c+d+e+f is less than 2, component (B) may volatilize as outgassing during heat curing of the adhesive composition, causing contamination, which is undesirable. On the other hand, if c+d+e+f is greater than 20, it becomes difficult to keep the viscosity value of the adhesive composition within a specific range, which is undesirable.

[0046] Examples of the monovalent perfluoropolyether group represented by the above general formula (5) include the following. [ka] (In the formula, b is an integer of 1 to 6; in formula (36), e' is an integer of 2 to 20; in formulas (37) to (40), d' is an integer of 2 to 20; in formula (41), e and f are each an integer of 0 to 20, and e+f is an integer of 2 to 20; and in formula (42), c' is an integer of 2 to 20.)

[0047] The monovalent perfluoropolyether group is bonded to a silicon atom in the (fluorine-containing) organohydrogenpolysiloxane compound, and a divalent linking group may be provided between the monovalent perfluoropolyether group and the silicon atom. The divalent linking group is any group selected from a divalent organic group having 1 to 6 carbon atoms, which may be connected via an ether bond or an amide bond, and a group represented by the following general formula (43A) and a group represented by the general formula (43B): [ka] (In the formula, Y 3 represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, h1 is 0 or 1, and h2 is an integer of 1 to 6. The bond marked with * indicates that it is bonded to the monovalent perfluoropolyether group represented by the above general formula (5) (the same applies hereinafter).

[0048] 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, of which -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, and groups represented by the following general formulas are preferred: In the following formulas, Me represents a methyl group. [ka]

[0049] The siloxane skeleton of the fluorine-containing organohydrogenpolysiloxane compound of component (B) may be cyclic, linear, branched, etc., but a fluorine-containing organohydrogenpolysiloxane compound having a cyclic siloxane skeleton is preferred. In particular, the fluorine-containing organohydrogenpolysiloxane compound of component (B) can be one represented by the following general formula (4):

[0050] [ka] (In the formula, R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and L 1 is a monovalent perfluoropolyether group represented by the above general formula (5), which may be bonded to a silicon atom via the above divalent linking group. w1 is an integer of 0 to 50, preferably an integer of 0 to 20, x1 is an integer of 2 to 50, preferably an integer of 3 to 20, and y1 is an integer of 1 to 50, preferably an integer of 1 to 20. Furthermore, w1+x1+y1 is an integer that satisfies the number average molecular weight of 1,000 to 4,000 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 ( ) above may be arranged randomly.

[0051] Above R 1 The unsubstituted or halogen-substituted monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenylethyl; and substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, and of these, methyl is particularly preferred.

[0052] The number average molecular weight of component (B) is 1 H-NMR and 19 When the structure of each component in ( ) in the general formula (4) and the structural unit contained in the general formula (5) are clear, the compound represented by the general formula (5) can be calculated by F-NMR measurement. 1 H-NMR measurement and 19 By performing F-NMR measurement, the number average molecular weight can be calculated from the integral value of each component in parentheses represented by general formula (4) and the integral value of each repeating unit represented by general formula (5).

[0053] Preferred examples of the component (B) having such a fluorine-containing organic group include the following compounds: In the following formula, Me represents a methyl group.

[0054] [ka] (In the formula, c' is an integer of 4 to 20.)

[0055] [ka] (In the formula, c' is an integer of 4 to 20.)

[0056] The amount of Si-H groups in component (B) is preferably 0.05 to 0.8 mol / 100 g, and more preferably 0.1 to 0.6 mol / 100 g. The amount of component (B) is an effective amount for curing component (A), and is usually an amount such that the hydrosilyl groups, i.e., Si-H groups, in component (B) are 0.1 to 2.5 moles, preferably 0.2 to 2 moles, per mole of alkenyl groups, such as vinyl groups, allyl groups, and cycloalkenyl groups, contained in component (A). If the amount of hydrosilyl groups (≡Si-H groups) is too small, the degree of crosslinking will be insufficient, and a cured product may not be obtained. If the amount is too large, foaming may occur during curing.

[0057] The total amount of Si-H groups in component (B) and component (D), which will be described later, is usually 0.105 to 4 mol, preferably 0.21 to 3 mol, and more preferably 0.41 to 2.5 mol per mol of alkenyl groups in component (A).

[0058] The composition of the present invention uses the fluorine-containing organohydrogenpolysiloxane compound having a mass loss rate of 20% or less as the fluorine-containing organohydrogenpolysiloxane compound of component (B) that acts as a crosslinking agent or chain extender for component (A). In a preferred embodiment, the cyclic fluorine-containing organohydrogenpolysiloxane compound having a mass loss rate of 15% or less can be used in combination with the fluorine-containing organohydrogenpolysiloxane compound having a linear siloxane structure having a mass loss rate of more than 15% (preferably a mass loss rate of about 16 to 20%, more preferably about 16 to 18%) in a proportion of the same mass or less (100% or less), particularly 75% or less (0 to 75% by mass), and even more particularly 55% or less (0 to 55% by mass), relative to the cyclic fluorine-containing organohydrogenpolysiloxane compound having a mass loss rate of 15% or less. This fluorine-containing organohydrogenpolysiloxane compound having a linear siloxane structure is also clearly distinguishable from the organohydrogenpolysiloxane compound serving as the adhesion promoter of component (D), described below, in that it does not contain functional groups in the molecule that can contribute to adhesion, such as epoxy groups and trialkoxysilyl groups. Preferred examples of this fluorine-containing organohydrogenpolysiloxane compound having a linear siloxane structure include the compounds shown below. In the following formula, Me represents a methyl group. [ka] (In the formula, i is an integer of 3 to 20, and c' is an integer of 2 to 20.)

[0059] Component (B) can be used singly or in combination of two or more. The fluorine-containing organohydrogenpolysiloxane compound of component (B) is clearly distinguishable from the organohydrogenpolysiloxane compound used as the adhesion promoter of component (D), described below, in that it does not contain functional groups in the molecule that can contribute to adhesion, such as epoxy groups and trialkoxysilyl groups.

[0060] [(C) component] Component (C) used in the adhesive composition of the present invention is a platinum group metal compound. This is a hydrosilylation catalyst that promotes the addition reaction between the alkenyl groups in component (A) and the hydrosilyl groups in components (B) and (D). This hydrosilylation catalyst is generally a noble metal compound and is expensive, so platinum or platinum compounds, which are relatively easy to obtain, are often used.

[0061] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. Compounds of platinum group metals other than 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, Pd(PPh3)4, etc. In the above formula, Ph is a phenyl group.

[0062] When using these catalysts, if they are solid catalysts they can be used in solid form, but in order to obtain a more uniform cured product, it is preferable to use a solution of chloroplatinic acid or a complex in an appropriate solvent, which is then mixed with the linear perfluoropolyether compound of component (A).

[0063] The amount of component (C) used may be a catalytic amount, but for example, it is preferably 0.1 to 1,000 ppm (platinum group metal atom equivalent) relative to the mass of component (A), and more preferably 1 to 500 ppm. Component (C) can be used alone or in combination of two or more different compounds.

[0064] [(D) component] Component (D) used in the adhesive composition of the present invention acts as an adhesion improver to fully develop self-adhesive properties in the composition of the present invention when incorporated therein. Component (D) is an organohydrogenpolysiloxane compound that contains, per molecule, at least one hydrogen atom bonded to a silicon atom (Si-H group) and at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and has a number average molecular weight of 700 or greater.

[0065] In the above-mentioned (D) component, it is more preferable that the compound further has one or more monovalent perfluoroalkyl groups or monovalent perfluoropolyether groups (perfluorooxyalkyl groups) bonded to silicon atoms via a divalent linking group containing at least one selected from nitrogen atoms, carbon atoms, and oxygen atoms in one molecule, preferably bonded to silicon atoms via a divalent linking group containing nitrogen atoms and carbon atoms, or bonded to silicon atoms via a divalent linking group containing nitrogen atoms, carbon atoms, and oxygen atoms. Such monovalent perfluoroalkyl groups or monovalent perfluoropolyether groups may be the same as those shown in the above-mentioned (B) component, and the divalent linking group connecting this monovalent perfluoroalkyl group or monovalent perfluoropolyether group to the silicon atom may also be the same as those shown in the above-mentioned (B) component.

[0066] The number-average molecular weight of component (D) is preferably 700 to 4,000, more preferably 900 to 2,000. If an organohydrogenpolysiloxane compound with a number-average molecular weight of less than 700 is present in the adhesive composition, it may volatilize as outgassing during heat curing, causing contamination, and it may be difficult to incorporate it in an amount sufficient to exhibit self-adhesion to various substrates, which is undesirable. On the other hand, organosiloxanes with a number-average molecular weight of more than 4,000 are undesirable because they significantly increase viscosity, making their incorporation difficult.

[0067] The siloxane skeleton of the organohydrogenpolysiloxane compound of component (D) may be cyclic, linear, branched, or the like, or may be a mixture of two or more of these. The organohydrogenpolysiloxane compound of component (D) can be one represented by the following general formula:

[0068] [ka] (In the formula, R 2 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and L 2 is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group as shown below, and M is an epoxy group or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom as shown below. w2 is preferably an integer satisfying 0≦w2≦50, more preferably an integer satisfying 0≦w2≦20, x2 is preferably an integer satisfying 1≦x2≦50, more preferably an integer satisfying 1≦x2≦20, y2 is preferably an integer satisfying 0≦y2≦50, more preferably an integer satisfying 1≦y2≦20, and z2 is preferably an integer satisfying 1≦z2≦50, more preferably an integer satisfying 1≦z2≦20. Furthermore, w2+x2+y2+z2 is an integer such that the number average molecular weight satisfies the above-mentioned range of 700 to 4,000. The repeating units in ( ) may be arranged randomly.

[0069] Above R 2 The unsubstituted or halogen-substituted monovalent hydrocarbon group is preferably one having 1 to 10 carbon atoms and not containing an aliphatic unsaturated bond, more preferably one having 1 to 8 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenylethyl; and substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, and of these, methyl is particularly preferred.

[0070] The above L 2is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group, and is preferably represented by the following general formula (44). -Z-Rf 3 (44) [In formula (44), Z is any group selected from a divalent organic group having 1 to 6 carbon atoms which may be bonded via an ether bond or an amide bond, a group represented by the following general formula (45), and a group represented by the following general formula (46), [ka] (In the formula, Y 4 is a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and j1 is an integer of 1 to 6. Note that a bond marked with an * indicates that it is bonded to a monovalent perfluoropolyether group (the same applies hereinafter). Rf 3 is a monovalent perfluoropolyether group.

[0071] Examples of Z include -CH2-*, -OCH2-*, -CHOCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -CH2-NH-CO-*, -(CH2)3-NH-CO-*, and groups represented by the following general formulae (45A), (45B), and (46A), of which -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, and groups represented by the general formulae (45A), (45B), or (46A) are preferred. In the following formulae, Me represents a methyl group. [ka]

[0072] In the above general formula (44), Rf 3 is a monovalent perfluoropolyether group and is represented by the following general formula (47): E1-(C4F8O) c1 -(C3F6O) d1 -(C2F4O) e1 -(CF2O) f1 -C g1 F 2g1 - (47) (E1 is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms; c1, d1, e1, and f1 each independently represent an integer of 0 to 20, and satisfy the condition 2≦c1+d1+e1+f1≦20; and g1 is an integer of 1 to 3. The repeating units in the above ( ) may be arranged randomly.)

[0073] Examples of the monovalent perfluoropolyether group represented by the above general formula (47) include the following. [ka] (In the formula, b1 is an integer of 1 to 6; in formula (48), e1' is an integer of 2 to 20; in formulas (49) to (52), d1' is an integer of 2 to 20; in formula (53), e1 and f1 are each an integer of 0 to 20, and e1+f1 is 2 to 20; and in formula (54), c1' is an integer of 2 to 20.)

[0074] The above M represents an epoxy group or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and specific examples thereof include the following groups.

[0075] [ka] (In the formula, R 3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, optionally containing an oxygen atom (such as an alkylene group such as a methylene group, an ethylene group, or a propylene group, a cycloalkylene group such as a cyclohexylene group, or an oxyalkylene group such as an oxyethylene group, an oxypropylene group, or an oxybutylene group, preferably -(CH2)3OCH2-*' (the bond with *' indicates a bond to an epoxy group)).

[0076] -R 4 -Si(OR 5 )3 (In the formula, R 4 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, especially 1 to 4 carbon atoms (e.g., an alkylene group such as a methylene group, an ethylene group, or a propylene group), and R5 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms (e.g., an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group).

[0077] [ka] (In the formula, R 6 is a hydrogen atom or a methyl group, and R 7 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms (e.g., an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group), and 1 represents an integer of 2 to 10.

[0078] The number average molecular weight of component (D) is 1 H-NMR and 19 This can be calculated by F-NMR measurement. When the structure of each component in ( ) in the above general formula representing component (D) and the structural unit contained in the above general formula (5) are clear, 1 H-NMR measurement and 19 By performing F-NMR measurement, the number average molecular weight can be calculated from the integral value of each component in parentheses in the above general formula representing component (D) and the integral value of each repeating unit represented by general formula (5).

[0079] The organohydrogenpolysiloxane compound of component (D) can be obtained by subjecting an organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms (Si-H groups) per molecule to a partial addition reaction, according to a conventional method, with a compound containing an aliphatic unsaturated group such as a vinyl group or an allyl group, an epoxy group and / or a trialkoxysilyl group, and optionally a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or a perfluorooxyalkyl group. Note that the number of aliphatic unsaturated groups must be less than the number of Si-H groups.

[0080] In producing the organohydrogenpolysiloxane compound of component (D), the target substance may be isolated after completion of the reaction, but it is also possible to use the mixture from which only the unreacted materials and addition reaction catalyst have been removed.

[0081] Specific examples of the organohydrogenpolysiloxane compound of component (D) include those represented by the following structural formula: These compounds may be used alone or in combination of two or more. In the following formula, Me represents a methyl group.

[0082] [ka] (In the formula, x2' is 2 or 3, and d1' is an integer of 2 to 20.)

[0083] [ka] (In the formula, x2' is 2 or 3, and d1' is an integer of 2 to 20.)

[0084] [ka] (In the formula, x2' is 1 or 2, and d1' is an integer of 2 to 20.)

[0085] [ka] (In the formula, z2' is 2 or 3, and d1' is an integer of 2 to 20.)

[0086] [ka] (In the formula, y2' is 2 or 3, and d1' is an integer of 2 to 20.)

[0087] The amount of Si-H groups in component (D) is preferably 0.06 to 0.6 mol / 100 g. The amount of component (D) to be added is such that the number of silicon-bonded hydrogen atoms in component (D) is 0.005 to 1.5 moles per mole of alkenyl groups in component (A), preferably 0.01 to 1.0 moles, and more preferably 0.05 to 0.5 moles. If the number of silicon-bonded hydrogen atoms in component (D) is less than 0.005 moles per mole of alkenyl groups in component (A), sufficient adhesion cannot be achieved. If the number of silicon-bonded hydrogen atoms in component (D) is more than 1.5 moles per mole of alkenyl groups in component (A), the flowability of the composition decreases, the physical strength of the resulting cured product decreases, and curing is often hindered, which is undesirable.

[0088] [(E) component] Component (E) is a carboxylic acid anhydride, an optional component that improves the adhesion-imparting ability of component (D) and promotes the self-adhesiveness of the cured product obtained by curing the composition of the present invention. As this component, those used as curing agents for epoxy resins can be used.

[0089] Examples of the carboxylic acid anhydride of component (E) include carboxylic acid anhydrides that are solid at 23° C. Specific examples include the following compounds: In the following formula, Me represents a methyl group. [ka]

[0090] The carboxylic acid anhydride of component (E) may also be a cyclic organopolysiloxane (i.e., a fluorine-containing organopolysiloxane-modified carboxylic acid anhydride compound) represented by the following general formula, which has in one molecule a hydrogen atom directly bonded to a silicon atom, a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may have an oxygen atom or a nitrogen atom, and a cyclic carboxylic acid anhydride residue bonded to a silicon atom via a divalent hydrocarbon group: [ka]

[0091] In the above formula, T' is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent hydrocarbon group which may have an oxygen atom or a nitrogen atom, and L of the above component (B) 1 These groups are introduced from the viewpoints of compatibility with component (A), dispersibility, uniformity after curing, and the like.

[0092] Also, R 21 is an unsubstituted or substituted monovalent hydrocarbon group, and R 1 The same groups as those listed above are exemplified, and a methyl group and an ethyl group are preferred.

[0093] Furthermore, t''' is an integer of 1 to 6, preferably an integer of 2 to 5, u''' is an integer of 1 to 4, preferably an integer of 1 to 3, v''' is an integer of 1 to 4, preferably an integer of 1 to 3, and t'''+u'''+v''' is an integer of 4 to 10, preferably an integer of 4 to 8, provided that ((H)(R 21 )SiO) units, ((T')(R 21 )SiO) units, and ((X')(R 21 The arrangement order of the SiO) units is random.

[0094] Furthermore, examples of the divalent hydrocarbon group, which may have an oxygen atom or a nitrogen atom, that connects the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group to the silicon atom include the same groups as the divalent linking groups exemplified for component (B) above.

[0095] X' is a cyclic carboxylic anhydride residue bonded to a silicon atom via a divalent hydrocarbon group, and specific examples include groups represented by the following general formula: [ka]

[0096] In the above formula, R 22is a divalent hydrocarbon group having 2 to 15 carbon atoms, and specific examples thereof include an ethylene group, a propylene group, and a butylene group, with a propylene group being preferred.

[0097] Examples of cyclic organopolysiloxanes represented by the above general formula include the following compounds: In the following formula, Me represents a methyl group. [ka] (In the formula, t1''' is 2 or 3, and c1' is an integer of 2 to 20.) [ka] (In the formula, V1''' is 2 or 3, and c1' is an integer of 2 to 20.)

[0098] These components (E) may be used alone or in combination of two or more, and in this case, the above-mentioned carboxylic acid anhydride that is solid at 23°C may be used in combination with the above-mentioned cyclic organopolysiloxane (fluorine-containing organopolysiloxane-modified carboxylic acid anhydride compound).

[0099] The amount of component (E) blended is 0.010 to 10 parts by mass, preferably 0.10 to 2 parts by mass, per 100 parts by mass of component (A). Amounts of 0.010 parts by mass or more are preferred because they are effective enough to promote the adhesive properties of the composition of the present invention. On the other hand, amounts of 10 parts by mass or less are preferred because they improve the flowability of the composition of the present invention and ensure storage stability.

[0100] [(F) Ingredients (other ingredients)] In order to enhance the practical utility of the adhesive composition of the present invention, various additives may be added as needed in addition to the above components (A) to (E), such as plasticizers, viscosity modifiers, flexibility-imparting agents, hydrosilylation reaction catalyst inhibitors, inorganic fillers, adhesion promoters, adhesion additives other than component (D), silane coupling agents, etc. The amounts of these additives added are arbitrary as long as they do not impair the object of the present invention and do not impair the characteristics of the composition or the physical properties of the cured product.

[0101] As a plasticizer, viscosity modifier, or flexibility-imparting agent, a polyfluoromonoalkenyl compound represented by the following general formula (55) and / or a linear polyfluoro compound represented by the following general formulas (56) and (57) can be used in combination. The number average molecular weight of these compounds is preferably 3,000 to 20,000.

[0102] Rf 4 -(X') p’ CH=CH2(55) [In formula (57), X' is the above L 2 is the same as Z (divalent linking group) in the structure, p' is 0 or 1, and Rf 4 is a monovalent perfluoropolyether group represented by the following general formula: [ka] (In the formula, f' is an integer of 2 to 200, preferably an integer of 2 to 100, h' is an integer of 1 to 3, and the sum of f' and h' is the Rf of the linear perfluoropolyether compound represented by the general formula (1) above. 1 is less than the sum of p and q in

[0103] Y 5 -O-(CF2CF2CF2O) c2 -Y 5 (56) [In the formula, Y 5 are independently of each other by the formula: C k' F 2k'+1 - (k' is an integer of 1 to 3), c2 is an integer of 1 to 200, and Rf of the linear perfluoropolyether compound represented by the general formula (1) 1 is smaller than z at .]

[0104] Y 6 -O-(CF2O) d2 (CF2CF2O) e2 -Y 6 (57) (In the formula, Y 6 is the above Y 5where d2 and e2 are each an integer of 1 to 200, and the sum of d2 and e2 is the Rf of the linear perfluoropolyether compound represented by the general formula (1) above. 1 The repeating units in ( ) above may be arranged randomly.

[0105] Specific examples of the polyfluoromonoalkenyl compound represented by the above general formula (55) include the following: In addition, the following m' satisfies the above requirements.

[0106] [ka]

[0107] Specific examples of the linear polyfluoro compounds represented by the above general formulas (56) and (57) include the following: Note that c2, d2, e2, and the sum of d2 and e2 below satisfy the above requirements. CF3O-(CF2CF2CF2O) c2 -CF2CF3 CF3-(OCF2CF2) e2 (OCF2) d2 -O-CF3

[0108] The amount of the polyfluoro compounds of the above formulas (55), (56), and (57) blended is 1 to 300 parts by mass, and preferably 50 to 250 parts by mass, per 100 parts by mass of component (A).The viscosity (23°C) should desirably be in the range of 2,000 to 50,000 mPa s.

[0109] Examples of inhibitors for hydrosilylation reaction catalysts include acetylenic alcohols such as ethynylcyclohexanol (also known as 1-ethynyl-1-hydroxycyclohexane), 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol; reaction products of the above-mentioned chlorosilanes having a monovalent fluorine-containing substituent with acetylenic alcohols; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and triallyl isocyanurate; polyvinyl siloxanes; and organic phosphorus compounds. The addition of these inhibitors can maintain appropriate curing reactivity and storage stability.

[0110] Examples of inorganic fillers that can be added include reinforcing or semi-reinforcing fillers such as quartz powder, fused quartz powder, diatomaceous earth, and calcium carbonate; inorganic pigments such as titanium oxide, iron oxide, carbon black, and cobalt aluminate; heat resistance improvers such as titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate; thermal conductivity imparting agents such as alumina, boron nitride, silicon carbide, and metal powder; and conductivity imparting agents such as carbon black, silver powder, and conductive zinc white.

[0111] In addition, an adhesion promoter such as a carboxylic acid anhydride or a titanate ester, an adhesion promoter other than component (D), and / or a silane coupling agent may be added.

[0112] [Method of manufacturing adhesive composition] The adhesive composition of the present invention can be produced by uniformly mixing the above-described components (A) to (D) and other optional components using a mixing device such as a planetary mixer, a Ross mixer, or a Hobart mixer, and, if necessary, a kneading device such as a kneader or a three-roll mill.

[0113] The method for producing the adhesive composition of the present invention is not particularly limited, and it can be produced by kneading the above-mentioned components. Alternatively, it may be produced as a two-part composition that is mixed at the time of use.

[0114] The adhesive composition produced can be cured at room temperature depending on the type of catalyst used as component (C), but it is preferable to heat it to accelerate curing. In order to achieve particularly 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.

[0115] When using the adhesive composition of the present invention, the composition may be dissolved to a desired concentration in an appropriate fluorine-based solvent, such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, etc., depending on the application and purpose, as long as the composition is not affected by outgassing during heat curing. The use of a solvent is particularly preferred for thin film coating applications.

[0116] The adhesive composition of the present invention exhibits good adhesion to a wide variety 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 plastics include epoxy resins, phenolic resins, polyester resins such as PET (polyethylene terephthalate) resin and 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 product of the adhesive composition of the present invention is preferably about 80 μm to 1 mm.

[0117] The adhesive composition of the present invention is also useful as an adhesive for various electrical and electronic components. For example, it can be suitably used as an adhesive for inkjet printers, an adhesive or sealant for printer heads, a coating agent for the rolls and belts of laser printers and copiers, an adhesive sealant or coating agent for various circuit boards, and a die attach material for the manufacture of in-vehicle sensors. Specifically, the adhesive composition of the present invention can be used to make a die attach material for in-vehicle sensors, or a protective sealant or coating agent for printing and copiers. These compositions can be used to manufacture in-vehicle sensor articles in which a sensor chip is fixed with a cured product of the adhesive composition of the present invention, or to manufacture parts for printing and copiers in which a protective seal or coating layer is formed from a cured product of the adhesive composition of the present invention. [Example]

[0118] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts refer to parts by mass. The viscosity and adhesive strength are measured at 23°C (the viscosity was measured in accordance with the rotational viscosity method of the viscosity test specified in JIS K6249, and the adhesive strength was measured in accordance with the tensile shear adhesive strength test method for adhesives to rigid adherends specified in JIS K6850). The (number average) molecular weights of compounds (58), (64), and (65) were determined as polystyrene-equivalent number average molecular weights in gel permeation chromatography (GPC) analysis using AK-225 (manufactured by Asahi Glass Co., Ltd.) as a fluorine-based solvent as a developing solvent. The (number average) molecular weights of compounds (59), (60), (61), (63), (66), and (67) were determined as follows: 1 H-NMR measurement and 19 F-NMR measurements were performed, and the amount of vinyl groups in the compound was calculated based on the integral value of each unit calculated from the spectrum obtained. Regarding the amount of vinyl groups in component (A), component (A1) was measured by infrared spectroscopy (IR) using a calibration curve, and components (A2), (A3), and (A4) were measured by proton nuclear magnetic resonance spectroscopy ( 1The amount of Si-H groups in the (B) components ((B1), (B2), and (B')) and the (D) components ((D1) and (D2)) was measured by proton nuclear magnetic resonance spectroscopy ( 1 H-NMR).

[0119] Furthermore, the mass loss rate of each of the following compounds when heated at 150° C. for 1 hour was determined by the following measurement method. First, the tare weight (W1) of a clean aluminum dish was weighed using a precision balance (reading limit 0.0001 mg). Next, 1.5 g of sample (compound) was placed on the aluminum dish, and the mass (W2) of the aluminum dish with the sample on it was weighed using a precision balance. Next, the aluminum dish with the sample on it was left in an incubator at 150 °C for 1 hour. After heating, the aluminum dish was removed from the incubator and allowed to cool in a desiccator. After cooling, the mass (W3) of the aluminum dish with the sample on it was weighed using a precision balance. The mass loss rate of this sample was calculated using the following formula. {(W3-W1) / (W2-W1)} x 100 (unit: %) W1: Mass of aluminum dish (g) W2: Mass of aluminum dish + mass of sample before heating (g) W3: Mass of aluminum dish + mass of sample after heating (g)

[0120] [Example 1] (A1) 100 parts of a polymer represented by the following formula (58) (number average molecular weight 15,550, mass reduction rate 0.5%, viscosity 10,900 mPa·s, vinyl group amount 0.012 mol / 100 g), (C1) 0.033 parts of an ethanol solution of a platinum-divinyltetramethyldisiloxane complex (platinum concentration 3.0 mass%), 0.25 parts of a 60 mass% toluene solution of ethynylcyclohexanol, (B1) a compound represented by the following formula (59) (number average molecular weight 15,550, mass reduction rate 0.5%, viscosity 10,900 mPa·s, vinyl group amount 0.012 mol / 100 g), An adhesive composition was prepared by mixing 3.00 parts of (B2) a compound represented by the following formula (60) (number average molecular weight 1,720, mass reduction rate 16.0%, Si-H group content 0.52 mol / 100 g), 1.52 parts of (B3) a compound represented by the following formula (60) (number average molecular weight 1,720, mass reduction rate 16.0%, Si-H group content 0.52 mol / 100 g), and 2.00 parts of (D1) a compound represented by the following formula (61) (number average molecular weight 990, Si-H group content 0.121 mol / 100 g). In the formula, Me represents a methyl group. [ka] (In the formula, m and n are integers of 1 or more, and the average value of m+n is 90.) [ka] (wherein the average value of c' is 8.) [ka] (wherein the average value of i=9.) [ka]

[0121] (Contamination confirmation test during heat curing) Next, the following experiment was carried out to confirm whether or not the composition would contaminate the surroundings due to outgassing when cured by heating. Four sensor chips were prepared, and a microscope was used to confirm that the gold pads on the sensor chips were not contaminated (before testing). The sensor chips were then placed in clean glass dishes, which were then covered and placed in an incubator at 150°C for one hour. After heating, the glass dishes were removed from the incubator and allowed to cool in a desiccator for three hours. The sensor chips were then removed from the glass dishes, and a microscope was used to confirm that the gold pads were not contaminated, just as they were before being placed in the incubator. Next, 10 g of the adhesive composition of Example 1 and four sensor chips were placed adjacent to each other in a clean glass petri dish, and after heating (leaving in a thermostatic oven at 150°C for 1 hour) and cooling (leaving in a desiccator for 3 hours) according to the method described above, the sensor chips after this test were removed and the degree of contamination of the gold pads was confirmed under a microscope. The results are shown in Table 1.

[0122] If the adhesive composition is outgassed during heat curing and the sensor chip is contaminated, the sensor chip will have a poor appearance (discoloration) due to the adhesion of outgassed components. Therefore, if the appearance of the sensor chip is almost the same as that of the blank, it can be said that the sensor chip is not contaminated by outgassing during heat curing of the composition.

[0123] [Example 2] An adhesive composition was prepared in the same manner as in Example 1, except that 0.2 parts of (E1) a compound represented by the following formula (62) was further added per 100 parts of (A1) a polymer represented by the above formula (58). This adhesive composition was subjected to a test to check for contamination during heat curing and evaluation in the same manner as in Example 1. The results are shown in Table 1. [ka]

[0124] [Example 3] 100 parts of the polymer (A1) represented by the above formula (58) and 6.3 parts of fumed silica (Aerosil R-972 (trade name, manufactured by Aerosil Co., Ltd.)) were kneaded using a planetary mixer at room temperature for 30 minutes, and then further kneaded under a reduced pressure of -98.0 kPaG at 150 ° C. for 1 hour. After cooling the kneaded mixture to room temperature, 0.033 parts of an ethanol solution of platinum-divinyltetramethyldisiloxane complex (C1) (platinum concentration 3.0 mass%), 0.25 parts of a 60 mass% toluene solution of ethynylcyclohexanol, 3.00 parts of the compound (B1) represented by the above formula (59), 1.52 parts of the compound (B2) represented by the above formula (60), 2.00 parts of the compound (D1) represented by the above formula (61), and 0.2 parts of the compound (E1) represented by the above formula (62) were added and mixed to prepare an adhesive composition. This adhesive composition was subjected to a contamination confirmation test and evaluation during heat curing in the same manner as in Example 1. The results are shown in Table 1.

[0125] [Example 4] In Example 3, an adhesive composition was prepared in the same manner as in Example 3, except that 0.20 parts of (D2) a compound represented by the following formula (63) (number average molecular weight 1,024, Si-H group amount 0.098 mol / 100 g) was further added per 100 parts of (A1) the polymer represented by the above formula (58). This adhesive composition was subjected to a test to check for contamination during heat curing and evaluation in the same manner as in Example 1. The results are shown in Table 1. In the formula, Me represents a methyl group. [ka]

[0126] [Example 5] An adhesive composition was prepared by mixing 100 parts of (A2) a polymer represented by the following formula (64) (number average molecular weight 6,450, mass loss rate 0.4%, viscosity 60 mPa·s, vinyl group content 0.031 mol / 100 g), (C1) 0.033 parts of an ethanol solution of a platinum-divinyltetramethyldisiloxane complex (platinum concentration 3.0 mass%), 0.25 parts of a 60 mass% toluene solution of ethynylcyclohexanol, (B1) 19.4 parts of a compound represented by the above formula (59), (B2) 1.79 parts of a compound represented by the above formula (60), (D1) 2.0 parts of a compound represented by the above formula (61), and (E1) 0.2 parts of a compound represented by the above formula (62). This adhesive composition was subjected to a contamination confirmation test and evaluation during heat curing in the same manner as in Example 1. The results are shown in Table 1. [ka] (In the formula, m and n are integers of 1 or more, and the average value of m+n is 34.)

[0127] [Example 6] An adhesive composition was prepared in the same manner as in Example 3, except that 100 parts of (A3) polymer represented by the following formula (65) (number average molecular weight 15,630, mass loss rate 0.4%, viscosity 11,000 mPa s, vinyl group content 0.012 mol / 100 g) were used instead of (A1) polymer represented by the above formula (58). This adhesive composition was subjected to a test to check for contamination during heat curing and evaluation in the same manner as in Example 1. The results are shown in Table 1. In the formula, Me represents a methyl group. [ka] (In the formula, m and n are integers of 1 or more, and the average value of m+n is 90.)

[0128] [Comparative Example 1] In Example 1, an adhesive composition was prepared in the same manner as in Example 1, except that 1.83 parts of (B') a compound represented by the following formula (66) (number average molecular weight 762, mass reduction rate 100%, Si-H group content 0.394 mol / 100 g) was used instead of (B1) a compound represented by the above formula (59), and (B2) a compound represented by the above formula (60) was changed to 1.18 parts. This adhesive composition was subjected to a test to check for contamination during heat curing and evaluation in the same manner as in Example 1. The results are shown in Table 1. In the formula, Me represents a methyl group. [ka]

[0129] Comparative Example 2 An adhesive composition was prepared in the same manner as in Example 1, except that 100 parts of (A4) polymer represented by the following formula (67) (number average molecular weight 1,810, mass loss rate 28%, viscosity 28 mPa s, vinyl group content 0.10 mol / 100 g) was used instead of 100 parts of polymer (A1) represented by the above formula (58). This adhesive composition was subjected to a test to check for contamination during heat curing and evaluation in the same manner as in Example 1. [ka] (In the formula, m and n are integers of 1 or more, and the average value of m+n is 9.)

[0130] [Table 1]

[0131] Figure 1 shows photographs of the appearance of the sensor chip in Example 1 before and after the contamination confirmation test during heat curing. The circular pattern in the center of the photograph in Figure 1 is the gold pad of the sensor chip. In Example 1, compared to the sensor chip in the pre-test (blank) state (Figure 1(a)), no discoloration or other appearance defects were observed in the sensor chip after the test (Figure 1(b)). Furthermore, similar to Example 1, no gold pad contamination (discoloration due to the adhesion of liquid or oily impurities to the gold pad) was observed on the sensor chip in Examples 2 to 6. On the other hand, Figure 2 shows photographs of the appearance of the sensor chip in Comparative Example 1 before and after the contamination confirmation test during heat curing. In Comparative Example 1, compared to the sensor chip in the pre-test (blank) state (Figure 2(a)), it was confirmed that the sensor chip after the test (Figure 2(b)) had discoloration due to the adhesion of liquid or oily impurities. In Comparative Example 2, similar to Comparative Example 1, gold pad contamination of the sensor chip was confirmed.

[0132] (Adhesion test) Two 100 mm × 25 mm test panels of various adherends (aluminum (Al), stainless steel (SUS), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS)) listed in Table 2 were overlapped by 10 mm at their edges, sandwiching a 1 mm-thick layer of each composition obtained in Examples 1 to 6 and Comparative Examples 1 and 2. The compositions were cured by heating at 150°C for 1 hour to prepare adhesive test specimens. These test specimens were then subjected to a tensile shear adhesion test (tensile speed 50 mm / min) to evaluate the adhesive strength (shear bond strength) and cohesive failure rate. The results are shown in Table 2. In the table, the values ​​in the top row represent shear bond strength, and the values ​​in parentheses in the bottom row represent the cohesive failure rate (%).

[0133] [Table 2]

Claims

1. (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and having a number average molecular weight of 2,000 or more; (B) a crosslinker component consisting of the following (B1) and (B2): (B1) A fluorine-containing organohydrogenpolysiloxane compound having a cyclic siloxane skeleton, which has two or more hydrogen atoms bonded to silicon atoms in each molecule, has one or more fluorine-containing organic groups, does not contain epoxy groups or trialkoxysilyl groups, and has a number average molecular weight of 1,000 or more and 4,000 or less; (B2) an organohydrogensiloxane compound that does not contain an epoxy group or a trialkoxysilyl group and that exhibits a mass loss rate of more than 15% when heated at 150°C for 1 hour; (C) a platinum group metal compound, and (D) An organohydrogenpolysiloxane compound having, in each molecule, at least one hydrogen atom bonded to a silicon atom and at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and having a number average molecular weight of 700 to 4,000. An electrical or electronic part having a cured product of an adhesive composition containing the adhesive composition.

2. 2. The electrical / electronic part according to claim 1, wherein the adhesive composition contains the component (B2) in an amount equal to or less than the mass of the component (B1).

3. 3. The electrical or electronic part according to claim 1, wherein the organohydrogensiloxane compound of component (B2) is a fluorine-containing organohydrogensiloxane compound.

4. 4. The electrical or electronic part according to claim 1, wherein the fluorine-containing organohydrogenpolysiloxane compound of component (B1) has a mass loss of 15% or less when heated at 150°C for 1 hour.

5. 5. The electric potential part according to claim 1, wherein the number average molecular weight of the compound of component (B) is smaller than the number average molecular weight of the linear perfluoropolyether compound of component (A).

6. 6. The electric / electronic part according to claim 1, wherein the linear perfluoropolyether compound of component (A) has a number average molecular weight of more than 4,000.

7. 7. The electric or electronic component according to claim 1, wherein component (B) is blended in an amount such that 0.1 to 2.5 moles of hydrogen atoms bonded to silicon atoms in component (B) per mole of alkenyl groups in component (A).

8. 8. The electric or electronic component according to claim 1, wherein component (D) is blended in an amount such that 0.005 to 1.5 moles of hydrogen atoms bonded to silicon atoms in component (D) per mole of alkenyl groups in component (A).

9. The electrical or electronic component according to any one of claims 1 to 8, characterized in that the adhesive composition is subjected to the following contamination confirmation test during heat curing, and no contamination of the gold pads on the sensor chip is confirmed by microscopic observation after the test. (Contamination confirmation test during heat curing) Four sensor chips were prepared, and the gold pads on the sensor chips were confirmed to be free of contamination using a microscope. The sensor chips were then placed in a clean glass dish, which was then covered and placed in an incubator at 150°C for one hour. After this heating, the glass dish was removed from the incubator and allowed to cool in a desiccator for three hours. The sensor chips were then removed from the glass dish, and the gold pads were confirmed to be free of contamination using a microscope, just as they were before being placed in the incubator. Next, 10 g of the sealant and four sensor chips were placed adjacent to each other in a clean glass petri dish, and after heating (leaving in a 150°C incubator for 1 hour) and cooling (leaving in a desiccator for 3 hours) according to the method described above, the sensor chips after the test were removed and the degree of contamination of the gold pads was checked under a microscope.

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