WO2022075245A1 - 接着剤組成物、ダイアタッチ材、保護用シール剤又はコーティング剤、及び電気・電子部品 - Google Patents
接着剤組成物、ダイアタッチ材、保護用シール剤又はコーティング剤、及び電気・電子部品 Download PDFInfo
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- WO2022075245A1 WO2022075245A1 PCT/JP2021/036571 JP2021036571W WO2022075245A1 WO 2022075245 A1 WO2022075245 A1 WO 2022075245A1 JP 2021036571 W JP2021036571 W JP 2021036571W WO 2022075245 A1 WO2022075245 A1 WO 2022075245A1
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- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
Definitions
- the present invention has less contamination of surrounding parts due to outgas generated during heat curing, firmly adheres to various substrates such as metal and plastic, and has solvent resistance, chemical resistance, heat resistance, and low temperature after curing.
- a perfluoropolyether-based adhesive composition that provides a fluoropolyether-based cured product having excellent properties, low moisture permeability, electrical properties, etc., a die-attaching material composed of the adhesive composition, a protective sealant or coating agent, and
- the present invention relates to an in-vehicle sensor component having a cured product of the adhesive composition, or an electrical / electronic component such as a printing / copying device or a fuel cell component.
- a curable fluoroelastomer composition utilizing an addition reaction between an alkenyl group and a hydrosilyl group is known, and further, as a third component (adhesion improving agent), a hydrosilyl group and an epoxy group and / or a trialkoxysilyl group are used.
- a composition to which self-adhesiveness is imparted by adding an organopolysiloxane having an elastomer to the composition has been proposed (Patent Document 1: Japanese Patent Application Laid-Open No. 9-9615).
- the composition can be cured by heating for a short time, and the obtained cured product (fluorinated elastomer cured product) has solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, electrical characteristics, etc. Because of its excellent properties, it is used for adhesive applications in various industrial fields where these properties are required.
- gaseous impurities are generated during heat curing of the composition, which contaminates peripheral parts and causes problems.
- the outgas gaseous fluorine-containing small molecule compound generated during heat curing contaminates the ink ejection path and the vicinity of the ejection port, and ejects ink.
- the sex changes.
- the gold pad on the chip is contaminated by contamination by outgas, and wire bonding is possible.
- This outgas is blended as an adhesion improver in addition to a perfluoropolyether compound having a low degree of polymerization in the main agent (base polymer) contained in the composition and a fluorine-containing organohydrogensiloxane which is a cross-linking agent. It is considered that the low molecular weight components such as the fluorine-containing organic compound or the non-fluorine-based organic compound volatilize from the composition before the curing reaction is completed by heating.
- the molecular weight of each of the fluorine-containing organic compound or the non-fluorine-based organic compound used as a component of the adhesiveness improving agent is 2,000 or more, and the volatile content at 105 ° C. It is known to use a very small amount of adhesive composition (Patent Document 2: Japanese Patent No. 4582287).
- the viscosity of the obtained perfluoropolyether-based adhesive composition is high and the finish is easy.
- the fluorine-containing elastomer cured product obtained by curing a perfluoropolyether-based adhesive composition containing a high-molecular-weight fluorine-containing component other than the base polymer is soft (to a low hardness) and easy to finish.
- the perfluoropolyether-based adhesive composition is used for fixing the sensor chip on the substrate, and the fluorine-containing elastomer cured product obtained from the perfluoropolyether-based adhesive composition is used.
- the chip cannot be firmly held due to the flexibility of the cured fluoroelastomer, which may make wire bonding difficult.
- an inorganic filler it is possible to increase the viscosity of the perfluoropolyether-based adhesive composition and improve the physical properties of the cured fluoroelastomer, but it may be difficult to develop adhesion to metals, resins, and the like. ..
- the perfluoropolyether-based adhesive composition it is preferable that some or all the components other than the base polymer have a relatively low molecular weight, and the perfluoro is less polluted by the outgas during curing.
- a polyether adhesive composition is required.
- the present invention has been made in view of the above circumstances, and has less contamination of surrounding parts due to outgas generated during heat curing, firmly adheres to various substrates such as metal and plastic, and is solvent resistant after curing.
- a perfluoropolyether-based adhesive composition that gives a cured product of a fluoropolymer having excellent properties, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, electrical characteristics, etc., and a die attach material comprising the adhesive composition.
- a protective sealant or coating agent comprising the adhesive composition, and an electric / electronic component having a cured product of the adhesive composition.
- the present inventors have a base polymer having a number average molecular weight of 2,000 or more and a small number of low molecular weight components that cause outgas, and a number average molecular weight of 1,000.
- a cross-linking agent having a value of 4,000 or less
- the number average molecular weight of the fluorine-containing organic compound or the non-fluorine-based organic compound, which is an adhesive improving agent is not 2,000 or more (specifically). Even if the adhesiveness improver is a relatively low molecular weight component of about 700 to 2,000), a perfluoropolyether adhesive composition with almost no contamination of surrounding parts by outgas during heat curing is available. It was found that it could be obtained, and the present invention was made.
- the present invention comprises the following adhesive composition, a die attach material composed of the adhesive composition, a protective sealant or coating agent composed of the adhesive composition, and a cured product of the adhesive composition.
- Linear perfluoropolyether compound with a reduction rate of 1% or less 100 parts by mass
- (B) One molecule has two or more hydrogen atoms bonded to silicon atoms, one or more fluorine-containing organic groups, does not contain epoxy groups and trialkoxysilyl groups, and has a number average molecular weight of 1,.
- Fluorine-containing organohydrogen polysiloxane compound having 000 or more and 4,000 or less, and (B) component alone having a mass reduction rate of 20% or less when heated at 150 ° C. for 1 hour:
- (A) component The amount of hydrogen atom bonded to the silicon atom in the component (B) is 0.1 to 2.5 mol with respect to 1 mol of the alkoxy group in the compound.
- an organohydrogen polysiloxane compound having at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom and an oxygen atom and having a number average molecular weight of 700 or more: among the components (A).
- An adhesive composition comprising an amount of hydrogen atoms bonded to silicon atoms in the component (D) of 0.005 to 1.5 mol with respect to 1 mol of the alkenyl group of.
- a 1 is a divalent organic group having 1 to 4 carbon atoms which may independently contain an ether bond and an amide bond, a group represented by the following general formula (2) and a general formula (3). It is one of the groups selected from the groups represented by (In the formula, Y 1 is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, 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 with * indicates that it binds to Rf 1.
- B is a carbon atom or a silicon atom
- X 1 is independent of each other, at least two are alkenyl groups
- the other X 1 is a hydrogen atom (only when B is a carbon atom) or a methyl group
- Rf. 1 is a divalent perfluoropolyether group.
- w1 is an integer of 0 to 50
- x1 is an integer of 2 to 50
- y1 is an integer of 1 to 50
- w1 + x1 + y1 is an integer satisfying a number average molecular weight of 1,000 to 4,000.
- the repeating units in () may be randomly arranged.
- E is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms, and c, d, e, and f are independently integers of 0 to 20, and 2 ⁇ c + d + e + f ⁇ 20.
- g is an integer of 1 to 3.
- the repeating unit in () above may be randomly arranged.
- the component (D) is a monovalent perfluoroalkyl group or a monovalent component bonded to a silicon atom via a divalent linking group containing at least one selected from a nitrogen atom, a carbon atom and an oxygen atom in one molecule.
- a die attach material comprising the adhesive composition according to any one of [1] to [7].
- a protective sealant or coating agent comprising the adhesive composition according to any one of [1] to [7].
- the protective sealant or coating agent according to [10] which is for a printing / copying device or a fuel cell.
- the electrical / electronic component according to [12] which is an article for an in-vehicle sensor in which a sensor chip is fixed with a cured product of an adhesive composition.
- the electrical / electronic component according to [12] which is a component for a printing / copying device or a component for a fuel cell in which a cured product of an adhesive composition is used as a protective seal or a coating layer.
- the adhesive composition of the present invention there is extremely little contamination of surrounding parts due to outgas generated during heat curing, strong adhesion to various substrates such as metal and plastic, and solvent resistance after curing. It is possible to provide a cured product having excellent chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, electrical characteristics and the like.
- the adhesive composition according to the present invention is characterized by containing the following components (A), (B), (C) and (D).
- the linear perfluoropolyether compound of the component (A) used in the adhesive composition of the present invention has at least two alkenyl groups in one molecule and has a number average molecular weight of 2,000 or more.
- A) The mass reduction rate of the component (A) when the component alone is heated at 150 ° C. for 1 hour is 1% or less, and preferably in the main chain as shown by the general formula (1) described later. It has a divalent perfluoroalkyl ether structure and acts as a main agent (base polymer) in the adhesive composition of the present invention.
- the degree of polymerization (or molecular weight) of the linear polyfluoro compound reflecting the number of repetitions of the perfluorooxyalkylene unit constituting the perfluoropolyether structure of the main chain is determined by, for example, a fluorosolvent.
- a fluorosolvent As a solvent, it can be determined as a polystyrene-equivalent number average degree of polymerization (or number average molecular weight) or the like in gel permeation chromatography (GPC) analysis.
- GPC gel permeation chromatography
- the number average degree of polymerization (or number average molecular weight) of the linear polyfluoro compound can also be calculated from 19 F-NMR.
- the component (A) has a number average molecular weight of 2,000 or more, particularly preferably 4,000 or more, obtained by the synthesis method described in JP-A-9-95615. ..
- the linear perfluoropolyether compound having a number average molecular weight of less than 2,000 is not preferable because it volatilizes itself as an outgas at a large rate during heat curing and causes contamination of surrounding parts.
- the upper limit of the number average molecular weight may be 50,000 or less, particularly about 20,000 or less.
- the linear perfluoropolyether compound of the component (A) has a mass reduction rate of 1% or less when the component (A) is heated alone at 150 ° C. for 1 hour (heat treatment at 150 ° C.).
- the mass reduction rate is preferably 0.5% or less.
- the mass reduction rate of the (A) linear perfluoropolyether compound by this 150 ° C. heat treatment is larger than 1% (particularly 1.0%), the adhesive composition containing the same at the time of heat curing Outgas is generated and causes pollution.
- the mass reduction rate can be obtained by the following measuring method.
- a tare (W1) of a clean aluminum dish is weighed using a precision balance (reading limit 0.0001 mg).
- the sample is collected on an aluminum plate, and the mass (W2) of the aluminum plate on which the sample is placed is weighed using a precision balance.
- the aluminum dish on which the sample is placed is left in an incubator (in the air) at 150 ° C. for 1 hour. After heating, remove this aluminum dish from the incubator and let it cool in a desiccator. After allowing to cool, the mass (W3) of the aluminum plate on which the sample is placed is weighed using a precision balance.
- the mass reduction rate of this sample is calculated from the following formula.
- W1 Aluminum dish mass
- W2 Aluminum dish mass + sample mass before heating
- W3 Aluminum dish mass + sample mass after heating
- the method for measuring the mass reduction rate is the same for the components (B) and (D) described later.
- the linear perfluoropolyether compound represented by the general formula (1) described later has at least a number average molecular weight of less than 2,000 among the perfluoropolyether compounds having a small degree of polymerization contained therein. May be inevitably included, which can cause outgassing.
- the component (A) from which the low molecular weight component has been removed is prepared by, for example, performing the following operation 1 as a pretreatment on the linear perfluoropolyether compound represented by the general formula (1) described later. You may.
- a linear perfluoropolyether compound preferably a linear perfluoropolyether compound represented by the general formula (1) described later, is preferably used at a pressure of 1,330 Pa or less, preferably 665 Pa or less, at 100 to 300 ° C., preferably. Is obtained by subjecting to a reduced pressure treatment at a temperature of 150 to 250 ° C. for 1 hour or longer, preferably 5 hours or longer.
- the component (A) is preferably a linear perfluoropolyether compound having a structure represented by the following general formula (1).
- “linearity” means that perfluorooxyalkylene units, which are repeating units constituting the perfluoropolyether structure of the main chain, are linearly bonded (connected) to each other.
- the individual perfluorooxyalkylene units themselves may have a branched structure such as, for example, [OCF 2 CF (CF 3 )] units.
- a 1 is a divalent organic group having 1 to 4 carbon atoms which may independently contain an ether bond and an amide bond, a group represented by the following general formula (2) and a general formula (3).
- Y 1 is a hydrogen atom, a methyl group, an ethyl group or a phenyl group
- Y 2 is a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group
- o is an integer of 1 to 6.
- the bond with * indicates that it binds to Rf 1.
- B is a carbon atom or a silicon atom
- X 1 is independent of each other, and at least 2 of X 1 existing in the molecule (3 at each end of the molecular chain) are alkenyl groups.
- the other X 1 is a hydrogen atom (only when B is a carbon atom) or a methyl group
- Rf 1 is a divalent perfluoropolyether group.
- a 1 is a divalent organic group having 1 to 4 carbon atoms which may contain an ether bond and an amide bond, a group represented by the following general formula (2), and a general formula (3). It is one of the groups selected from the represented groups.
- Y 1 is a hydrogen atom, a methyl group, an ethyl group or a phenyl group
- Y 2 is a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group
- o is an integer of 1 to 6.
- the bond with * indicates that it binds to Rf 1 (the same applies hereinafter).
- Examples of A 1 include -CH 2- *, -OCH 2- *, -CH 2 CH 2 OCH 2- *, -CH 2 -NH-CO- *, and -CH 2 CH 2 -NH-CO- *.
- -CH 2 -NCH 3 -CO- * groups represented by the following general formulas (2A), (2B), (2C), (3A), (3B) and (3C), among which general formulas are mentioned.
- the group represented by (2A) or (3A) is preferable.
- Me is a methyl group and Et is an ethyl group.
- B is a carbon atom or a silicon atom.
- a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group and the like can be mentioned, and a vinyl group and an allyl group are preferable.
- X 1 is not an alkenyl group, it has a structure in which either a hydrogen atom or a methyl group is formed when B is a carbon atom and a methyl group is formed when B is a silicon atom.
- Rf 1 is a divalent perfluoropolyether group and contains a repeating unit of —C a F 2a O— (where a is an integer of 1 to 6). Examples thereof include those represented by the following formula (6). -(C a F 2a O) x- (6) (In the equation (6), a is an integer of 1 to 6, x is an integer of 5 to 600, preferably an integer of 10 to 400, and more preferably an integer of 30 to 200.)
- Examples of the repeating unit represented by the above formula-C a F 2a O- include units represented by the following formula. -CF 2 O- -CF 2 CF 2 O- -CF 2 CF 2 CF 2 O- -CF (CF 3 ) CF 2 O- -CF 2 CF 2 CF 2 O- -CF 2 CF 2 CF 2 CF 2 O-
- the repeating unit in the divalent perfluoropolyether group may be composed of one of these groups alone or in combination of two or more.
- the divalent perfluoropolyether group preferably contains the structures of the following formulas (7) to (11).
- D is a fluorine atom or a trifluoromethyl group
- p, q and r are p ⁇ 0, q ⁇ 0, 0 ⁇ p + q ⁇ 200, in particular 2 ⁇ p + q ⁇ 150 and 0 ⁇ r ⁇ 6.
- p + q 0, 1 ⁇ r ⁇ 6
- k, a', s, t and u are 1 ⁇ k ⁇ 3, 2 ⁇ a' ⁇ 6, 0 ⁇ s ⁇ 100, respectively.
- the component (A) represented by the general formula (1) when B is a carbon atom, the component represented by the following formula is suitable.
- M is an integer of 1 to 100
- n is an integer of 1 to 100
- m + n is an integer of 2 to 200.
- the alkenyl group content contained in the linear perfluoropolyether compound of the above formula (1) is preferably 0.002 to 0.3 mol / 100 g, more preferably 0.008 to 0.12 mol / 100 g. If the alkenyl group content contained in the linear perfluoropolyether compound is less than 0.002 mol / 100 g, the degree of cross-linking is insufficient and curing problems may occur, which is not preferable. If the amount is more than 0.3 mol / 100 g, the mechanical properties of the cured product as a rubber elastic body may be impaired, which is not preferable.
- the viscosity (23 ° C.) of the linear perfluoropolyether compound (A) is 40 to 100,000 mPa ⁇ s, more preferably 50 to 50,000 mPa ⁇ s, still more preferably 60 to 20,000 mPa ⁇ s. It is desirable that the composition is within the above range because the cured product also has appropriate physical properties when the composition of the present invention is used for sealing, potting, coating, impregnation and the like. Within the viscosity range, the most appropriate viscosity can be selected according to the application.
- the viscosity (23 ° C.) can be measured with a rotary viscometer or the like (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.) (same in Examples).
- these linear perfluoropolyether compounds can be used alone or in combination of two or more.
- the component (B) used in the adhesive composition of the present invention has two or more hydrogen atoms (Si—H groups) bonded to silicon atoms in one molecule, and has one or more fluorine-containing organic groups. , Epoxide group and trialkoxysilyl group are not contained, the number average molecular weight is 1,000 or more and 4,000 or less, and the mass reduction rate of the component (B) when the component (B) alone is heated at 150 ° C. for 1 hour. It is a fluorine-containing organohydrogen polysiloxane compound having a content of 20% or less, and functions as a cross-linking agent or a chain length extender for the component (A).
- the number average molecular weight of the component (B) is 1,000 to 4,000, preferably 1,000 to 2,500.
- Fluorine-containing organohydrogen polysiloxane compounds having a number average molecular weight of less than 1,000 are not preferable because when they are present in the adhesive composition, they volatilize as outgas themselves during heat curing and cause contamination.
- the fluorine-containing organohydrogen polysiloxane compound having a number average molecular weight of more than 4,000 the viscosity of the compound itself is easily reflected in the adhesive composition, and the viscosity value of the adhesive composition is kept within a specific range. It is not preferable because it is difficult to fit it.
- the fluorine-containing organohydrogen polysiloxane compound of the component (B) has a mass reduction rate of 20% or less when the component (B) alone is heated at 150 ° C. for 1 hour (heat treatment at 150 ° C.). This mass reduction rate is preferably 15% or less, and more preferably 8% or less.
- the mass reduction rate of the fluorine-containing organohydrogen polysiloxane compound is larger than 20%, outgas may be generated from the adhesive composition containing the fluorine-containing organohydrogen polysiloxane compound during heat curing, which may cause contamination of surrounding parts, which is not preferable.
- the mass reduction rate of the component (A) when the component (A) alone is heated at 150 ° C. for 1 hour is 1% (particularly 1.0%) or less, and It is necessary that the mass reduction rate of the component (B) when the component (B) alone is heated at 150 ° C. for 1 hour is 20% or less. As a result, it is possible to suppress the generation of outgas during heat curing of the adhesive composition of the present invention and prevent contamination.
- the fluorine-containing organic group in the molecule is one or more perfluoro in one molecule.
- Those having an alkyl group, a perfluorooxyalkyl group (monovalent perfluoropolyether group), a perfluoroalkylene group, a perfluorooxyalkylene group (divalent perfluoropolyether group) and the like are more preferable.
- the component (B) preferably has a monovalent perfluoropolyether group represented by the following general formula (5).
- E is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms
- c, d, e, and f are independently integers of 0 to 20, and 2 ⁇ c + d + e + f ⁇ 20.
- g is an integer of 1 to 3.
- the repeating unit in () above may be randomly arranged.
- Examples of the monovalent perfluoropolyether group represented by the general formula (5) include the following.
- b is an integer of 1 to 6, in equation (36), e'is an integer of 2 to 20, and in equations (37) to (40), d'is an integer of 2 to 20.
- e and f are integers of 0 to 20, respectively, e + f is an integer of 2 to 20, and in equation (42), c'is an integer of 2 to 20.
- the monovalent perfluoropolyether group is one that is bonded to a silicon atom in the (fluorine-containing) organohydrogenpolysiloxane compound, and 2 between the monovalent perfluoropolyether group and the silicon atom. It may be provided with a valence linking group.
- a divalent organic group having 1 to 6 carbon atoms which may be via 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) are represented. It is one of the groups selected from the groups to be.
- Y 3 is 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 with * is the above general. It is shown that it binds to a monovalent perfluoropolyether group represented by the formula (5) (hereinafter, the same applies).
- Examples of such a divalent linking group include -CH 2- *, -OCH 2- *,-(CH 2 ) 2 OCH 2- *,-(CH 2 ) 3 OCH 2- *,-(CH). 2 ) 3 -NH-CO- *,-(CH 2 ) 3 -NCH 3 -CO- *, groups represented by the following general formulas are mentioned, among which-(CH 2 ) 3 OCH 2- *,-( CH 2 ) 3 -NH-CO- *, any of the groups represented by the following general formula is preferable.
- Me represents a methyl group.
- the siloxane skeleton of the fluorine-containing organohydrogen polysiloxane compound of the component (B) may be cyclic, linear, branched, etc., but is a fluorine-containing organohydrogen polysiloxane compound having a cyclic siloxane skeleton. It is preferable to have.
- a compound represented by the following general formula (4) can be used as the fluorine-containing organohydrogen polysiloxane compound of the component (B).
- R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and L 1 may be bonded to a silicon atom via the above-mentioned divalent linking group. It is a monovalent perfluoropolyether group.
- W1 is an integer of 0 to 50, preferably an integer of 0 to 20, and x1 is an integer of 2 to 50, preferably 3 to 20.
- y1 is an integer of 1 to 50, preferably an integer of 1 to 20, and w1 + x1 + y1 is an integer satisfying the number average molecular weight of 1,000 to 4,000 as described above.
- the repeating units of the above () may be randomly arranged.
- the unsubstituted or halogen-substituted monovalent hydrocarbon group of R 1 those having 1 to 10 carbon atoms are preferable, those having 1 to 8 carbon atoms are more preferable, and specifically, a methyl group, an ethyl group and a propyl group.
- Alkyl groups such as groups, butyl groups, hexyl groups, cyclohexyl groups and octyl groups; aryl groups such as phenyl groups and trill groups; aralkyl groups such as benzyl groups and phenylethyl groups, and some of the hydrogen atoms of these groups.
- a substituted monovalent hydrocarbon group in which the whole is substituted with a halogen atom such as fluorine can be mentioned, and among these, a methyl group is particularly preferable.
- the number average molecular weight of the components can be calculated by 1 H-NMR and 19 F-NMR measurements.
- 1 H-NMR measurement of the compound represented by the general formula (5) and 19 By performing F-NMR measurement, the number average molecular weight can be obtained from the integrated value of each component in () represented by the general formula (4) and the integrated value of each repeating unit represented by the general formula (5). Can be calculated.
- the component (B) having such a fluorine-containing organic group for example, the following compounds are preferable examples.
- Me represents a methyl group.
- the amount of Si—H group of the component (B) is preferably 0.05 to 0.8 mol / 100 g, particularly preferably 0.1 to 0.6 mol / 100 g.
- the blending amount of the component (B) is an effective amount for curing the component (A), and is (B) with respect to 1 mol of an alkenyl group such as a vinyl group, an allyl group, or a cycloalkenyl group usually contained in the component (A).
- the amount of the hydrosilyl group, that is, the Si—H group in the component is 0.1 to 2.5 mol, preferably 0.2 to 2 mol.
- the total amount of Si—H groups of the component (B) and the component (D) described later is usually 0.105 to 4 mol with respect to 1 mol of the alkenyl group in the component (A).
- the amount is preferably 0.21 to 3 mol, more preferably 0.41 to 2.5 mol.
- composition of the present invention contains fluorine having a mass reduction rate of 20% or less as the fluorine-containing organohydrogenpolysiloxane compound of the component (B) that acts as a cross-linking agent or a chain length extender of the component (A).
- Organohydrogen polysiloxane compounds are used, but as a preferred embodiment, a cyclic fluorine-containing organohydrogenpolysiloxane compound having a mass reduction rate of 15% or less and a mass reduction rate of 15% or more are used.
- a fluorine-containing organohydrogen polysiloxane compound having a large (preferably 16 to 20%, more preferably 16 to 18% mass reduction rate) linear siloxane structure is used as a cyclic compound having a mass loss rate of 15% or less.
- a ratio of the same mass 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) with respect to the fluorine-containing organohydrogen polysiloxane compound. Can be used together.
- the fluorine-containing organohydrogen polysiloxane compound having a linear siloxane structure will also be described later in that it does not have a functional group in the molecule that can contribute to adhesion such as an epoxy group and a trialkoxysilyl group.
- D It is clearly distinguished from the organohydrogen polysiloxane compound which is the adhesive-imparting agent of the component.
- the fluorine-containing organohydrogen polysiloxane compound having this linear siloxane structure for example, the compounds shown below are preferable examples.
- Me represents a methyl group.
- i is an integer of 3 to 20 and c'is an integer of 2 to 20.
- the component (B) can be used alone or in combination of two or more.
- the fluorine-containing organohydrogen polysiloxane compound of the component (B) will be described later in that it does not have a functional group such as an epoxy group or a trialkoxysilyl group in the molecule, which can contribute to the adhesiveness.
- D) It is clearly distinguished from the organohydrogen polysiloxane compound, which is an adhesive-imparting agent for the component.
- the component (C) used in the adhesive composition of the present invention is a platinum group metal compound.
- This is a hydrosilylation reaction catalyst, which is a catalyst that promotes the addition reaction between the alkenyl group in the component (A) and the hydrosilyl group in the components (B) and (D).
- This hydrosilylation reaction catalyst is generally a compound of a noble metal, and since it is expensive, platinum or a platinum compound which is relatively easily available is often used.
- platinum compound examples include platinum chloride or a complex of platinum chloride and an olefin such as ethylene, a complex of alcohol or vinylsiloxane, and metallic platinum supported on silica, alumina, carbon or the like.
- Rhodium, ruthenium, iridium, and palladium-based compounds are also known as platinum group metal compounds other than platinum compounds.
- RhCl (PPh 3 ) 3 , RhCl (CO) (PPh 3 ) 2 , Ru 3 (CO) 12 , IrCl (CO) (PPh 3 ) 2 , Pd (PPh 3 ) 4 , and the like can be exemplified.
- Ph is a phenyl group.
- platinum chloride acid or a complex is dissolved in an appropriate solvent. It is preferable to dissolve the compound in the linear perfluoropolyether compound of the component (A) before use.
- the amount of the component (C) used may be a catalytic amount, but for example, 0.1 to 1,000 ppm (in terms of platinum group metal atom) is preferably added to the mass of the component (A), and 1 to 500 ppm is preferable. More preferred.
- the component (C) can be used alone or in combination of two or more.
- the component (D) used in the adhesive composition of the present invention acts as an adhesiveness improving agent for sufficiently developing self-adhesiveness in the composition of the present invention by blending the component (D).
- the molecule has one or more hydrogen atom (Si—H group) bonded to the silicon atom and one or more epoxy group and / or trialkoxysilyl group bonded to the silicon atom via the carbon atom or the carbon atom and the oxygen atom. It is an organohydrogen polysiloxane compound having a number average molecular weight of 700 or more.
- a nitrogen atom and a carbon atom bonded to a silicon atom via a divalent linking group containing at least one selected from a nitrogen atom, a carbon atom and an oxygen atom in one molecule preferably a nitrogen atom and a carbon atom bonded to a silicon atom via a divalent linking group containing at least one selected from a nitrogen atom, a carbon atom and an oxygen atom in one molecule.
- a monovalent perfluoroalkyl group or monovalent bonded to a silicon atom via a divalent linking group containing or via a divalent linking group containing a nitrogen atom, a carbon atom and an oxygen atom Those having one or more perfluoropolyether groups (perfluorooxyalkyl groups) are more preferable.
- Such a monovalent perfluoroalkyl group or a monovalent perfluoropolyether group may be the same as that shown in the above component (B), and the monovalent perfluoroalkyl group or the monovalent per.
- the divalent linking group connecting the fluoropolyether group and the silicon atom may be the same as that shown in the above component (B).
- the number average molecular weight of the component (D) is preferably 700 to 4,000, more preferably 900 to 2,000.
- the organohydrogenpolysiloxane compound having a number average molecular weight of less than 700 it may volatilize as outgas itself during heat curing and cause contamination, and is self-adhesive to various substrates. It may be difficult to formulate a sufficient amount to express the above, which is not preferable.
- the organosiloxane having a number average molecular weight of more than 4,000 is not preferable because the viscosity increases significantly and compounding becomes difficult.
- the siloxane skeleton of the organohydrogen polysiloxane compound (D) may be cyclic, linear, branched, or the like, or may be a mixed form of two or more of these.
- organohydrogen polysiloxane compound of the component (D) a compound represented by the following general formula can be used.
- R 2 is an unsubstituted or halogen-substituted monovalent hydrocarbon group
- L 2 is a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group shown below.
- M is an epoxy group or a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom shown below.
- W2 is preferably an integer satisfying 0 ⁇ w2 ⁇ 50, and more preferably.
- w2 ⁇ 20 is an integer
- x2 is preferably an atom that satisfies 1 ⁇ x2 ⁇ 50, more preferably 1 ⁇ x2 ⁇ 20
- y2 is preferably 0 ⁇ y2 ⁇ 50. It is an integer that satisfies, more preferably an atom that satisfies 1 ⁇ y2 ⁇ 20,
- z2 is preferably an integer that satisfies 1 ⁇ z2 ⁇ 50, and more preferably an integer that satisfies 1 ⁇ z2 ⁇ 20.
- the repeating units of the above () may be randomly arranged.
- those containing no aliphatic unsaturated bond having 1 to 10 carbon atoms are preferable, those having 1 to 8 carbon atoms are more preferable, and specifically, those having 1 to 8 carbon atoms are more preferable.
- Is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group and an octyl group; an aryl group such as a phenyl group and a trill group; an aralkyl group such as a benzyl group and a phenylethyl group, and these.
- Examples thereof include a substituted monovalent hydrocarbon group in which a part or all of the hydrogen atom of the group is substituted with a halogen atom such as fluorine, and among these, a methyl group is particularly preferable.
- L 2 is 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 the formula (44), Z is a divalent organic group having 1 to 6 carbon atoms which may be via an ether bond or an amide bond, a group represented by the following general formula (45), and a general formula (46).
- 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 the bond with * is bonded to a monovalent perfluoropolyether group. Indicates that (the same shall apply hereinafter).
- Rf 3 is a monovalent perfluoropolyether group. ]
- -CH 2- *, -OCH 2- *, -CH 2 OCH 2- *,-(CH 2 ) 2 OCH 2- *,-(CH 2 ) 3 OCH 2- *, -CH 2 -NH-CO- *,-(CH 2 ) 3 -NH-CO- *, groups represented by the following general formulas (45A), (45B) and (46A) can be mentioned, among which-(CH 2 ).
- Me represents a methyl group.
- Rf 3 is a monovalent perfluoropolyether group and is represented by the following general formula (47).
- E1 is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms, and c1, d1, e1 and f1 are independently integers of 0 to 20, and 2 ⁇ c1 + d1 + e1 + f1 ⁇ 20.
- G1 is It is an integer of 1 to 3.
- the repeating unit in () above may be randomly arranged.
- Examples of the monovalent perfluoropolyether group represented by the general formula (47) include the following.
- b1 is an integer of 1 to 6
- e1' is an integer of 2 to 20 in the equation (48)
- d1' is an integer of 2 to 20 in the equations (49) to (52).
- e1 and f1 are integers of 0 to 20, respectively, e1 + f1 is 2 to 20, and in equation (54), c1'is an integer of 2 to 20.
- the above M represents an epoxy group or a 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.
- R 3 has 1 to 10 carbon atoms in which an oxygen atom may intervene, particularly a divalent hydrocarbon group having 1 to 5 carbon atoms (alkylene group such as methylene group, ethylene group, propylene group, cyclohexylene). Cycloalkylene groups such as groups, oxyethylene groups, oxypropylene groups, oxyalkylene groups such as oxybutylene groups, etc., preferably-(CH 2 ) 3 OCH 2- *'(*' Bonds are bonded to epoxy groups. Indicates that)) is indicated.)
- R 4 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms (alkylene group such as methylene group, ethylene group, propylene group, etc.), and R 5 has an independent carbon number. 1 to 8, particularly monovalent hydrocarbon groups having 1 to 4 carbon atoms (alkyl groups such as methyl group, ethyl group, propyl group, butyl group, etc.) are shown.)
- R 6 is a hydrogen atom or a methyl group
- R 7 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group). , Etc.), where l is an integer of 2-10.
- the number average molecular weight of the component (D) can be calculated by 1 H-NMR and 19 F-NMR measurements.
- (D) When the structure of each component in () in the above general formula representing the component and the structural unit contained in the above general formula (5) are clear, 1 H-NMR measurement and 19 F-NMR measurement should be performed. Then, the number average molecular weight can be calculated from the integral value of each component in () represented by the above general formula representing the component (D) and the integral value of each repeating unit represented by the general formula (5). can.
- the organohydrogen polysiloxane compound of the component (D) is an organohydrogenpolysiloxane having three or more hydrogen atoms (Si—H groups) bonded to silicon atoms in one molecule, and is not aliphatic such as vinyl group and allyl group.
- a compound containing a saturated group and an epoxy group and / or a trialkoxysilyl group, and if necessary, a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or a perfluorooxyalkyl group is partially added according to a conventional method. It can be obtained by letting it.
- the number of the aliphatic unsaturated groups needs to be smaller than the number of Si—H groups.
- the target substance may be isolated after the reaction is completed, but a mixture in which the unreacted substance and the addition reaction catalyst are simply removed can also be used.
- organohydrogen polysiloxane compound as the component (D) include those represented by the following structural formulas. These compounds may be used alone or in combination of two or more. In the following formula, Me represents a methyl group.
- the amount of Si—H group of the component (D) is preferably 0.06 to 0.6 mol / 100 g.
- the blending amount of the component (D) is preferably an amount in which the hydrogen atom bonded to the silicon atom in the component (D) is 0.005 to 1.5 mol with respect to 1 mol of the alkenyl group in the component (A).
- the amount is 0.01 to 1.0 mol, more preferably 0.05 to 0.5 mol.
- the fluidity of the composition deteriorates and the physical strength of the obtained cured product decreases. In addition, it is not preferable because it often inhibits curability.
- the component (E) is a carboxylic acid anhydride, which is optional for improving the adhesive-imparting ability of the component (D) and promoting the self-adhesive development of the cured product obtained by curing the composition of the present invention. It is an ingredient.
- the component those used as a curing agent for epoxy resins can be used.
- Examples of the carboxylic acid anhydride of the component (E) include a solid carboxylic acid anhydride at 23 ° C. Specific examples thereof include the following compounds. In the following formula, Me represents a methyl group.
- the carboxylic acid anhydride of the component (E) may have a hydrogen atom directly connected to a silicon atom and an oxygen atom or a nitrogen atom in one molecule represented by the following general formula. It has a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a hydrogen group, and a cyclic anhydrous carboxylic acid residue bonded to a silicon atom via a divalent hydrocarbon group. It may be a cyclic organopolysiloxane (that is, a fluorine-containing organopolysiloxane modified anhydrous carboxylic acid compound).
- 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 1 of the component (B) above.
- the same group as. are the groups introduced from the viewpoint of compatibility with the component (A), dispersibility, uniformity after curing, and the like.
- R 21 is an unsubstituted or substituted monovalent hydrocarbon group, and examples thereof include the same groups as R 1 described above, and a methyl group and an ethyl group are preferable.
- 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.
- t'''+ u'''+ v'' is an integer of 4 to 10, preferably an integer of 4 to 8.
- the arrangement order of the ((H) (R 21 ) SiO) unit, the ((T') (R 21 ) SiO) unit, and the ((X') (R 21 ) SiO) unit is random.
- the divalent hydrocarbon group which may have an oxygen atom or a nitrogen atom connecting the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group and the silicon atom is the above-mentioned component (B).
- Examples thereof include groups similar to the exemplified divalent linking group.
- X' is a cyclic anhydrous carboxylic acid residue bonded to a silicon atom via a divalent hydrocarbon group, and specific examples thereof include a group represented by the following general formula.
- R 22 is 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, and a propylene group is preferable.
- Examples of the cyclic organopolysiloxane represented by the above general formula include the following compounds.
- Me represents a methyl group.
- t1''' is an integer of 2 or 3
- c1' is an integer of 2 to 20.
- V1''' is an integer of 2 or 3
- c1' is an integer of 2 to 20.
- the blending amount of the component (E) is 0.010 to 10 parts by mass, preferably 0.10 to 2 parts by mass with respect to 100 parts by mass of the component (A).
- it is 0.010 part by mass or more, it is preferable because a sufficient effect can be obtained to promote the development of adhesiveness of the composition of the present invention.
- the amount is 10 parts by mass or less, the fluidity of the composition of the present invention is improved and the storage stability of the composition is obtained, which is preferable.
- a plasticizer in addition to the above components (A) to (E), a plasticizer, a viscosity modifier, a flexibility-imparting agent, and a hydrosilylation reaction catalyst are controlled.
- Various compounding agents such as an agent, an inorganic filler, an adhesion accelerator, an adhesive additive other than the component (D), and a silane coupling agent can be added as needed.
- the blending amount of these additives is arbitrary as long as the object of the present invention is not impaired and the characteristics of the composition and the physical properties of the cured product are not impaired.
- a plasticizer As a plasticizer, a viscosity modifier, and a flexibility-imparting agent, a polyfluoromonoalkenyl compound represented by the following general formula (55) and / or a linear poly represented by the following general formulas (56) and (57). Fluoro compounds can be used in combination.
- the number average molecular weight of these compounds is preferably 3,000 to 20,000.
- Rf 4- (X') p'CH CH 2 (55) [In formula (57), X'is the same as Z (divalent linking group) in the above L 2 structure, p'is 0 or 1, and Rf 4 is monovalent represented by the following general formula.
- Perfluoropolyether group (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 above general formula (1). ) Is smaller than the sum of p and q in Rf 1 of the linear perfluoropolyether compound represented by)]].
- Y 5 is a group independently represented 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 the above. It is smaller than z in Rf 1 of the linear perfluoropolyether compound represented by the general formula (1). ]
- Y 6 is the same as Y 5
- d2 and e2 are integers of 1 to 200, respectively
- the sum of d2 and e2 is a linear chain represented by the general formula (1). It is smaller than the sum of n and m in Rf 1 of the perfluoropolyether compound.
- the repeating unit in () above may be randomly arranged.
- polyfluoromonoalkenyl compound represented by the above general formula (55) include the following.
- linear polyfluoro compound represented by the general formulas (56) and (57) include the following.
- the blending amount of the polyfluoro compound of the above formulas (55), (56) and (57) is 1 to 300 parts by mass, preferably 50 to 250 parts by mass with respect to 100 parts by mass of the component (A).
- the viscosity (23 ° C.) is preferably in the range of 2,000 to 50,000 mPa ⁇ s.
- Examples of the regulator of the hydrosilylation reaction catalyst include ethynylcyclohexanol (also known as 1-ethynyl-1-hydroxycyclohexane), 3-methyl-1-butyne-3-ol, and 3,5-dimethyl-1-hexin.
- a acetylene alcohol such as -3-ol, 3-methyl-1-penten-3-ol, phenylbutynol, or a reaction product of the above-mentioned chlorosilane having a monovalent fluorine-containing substituent and an acetylene alcohol, 3-methyl.
- Examples thereof include -3-penten-1-in, 3,5-dimethyl-3-hexene-1-in, triallyl isocyanurate, polyvinylsiloxane, organic phosphorus compounds, etc., and the addition thereof provides curing reactivity and storage stability.
- the sex can be kept moderate.
- the inorganic filler examples include reinforcing or semi-reinforcing fillers such as quartz powder, molten quartz powder, diatomaceous earth and calcium carbonate, inorganic pigments such as titanium oxide, iron oxide, carbon black and cobalt aluminate, titanium oxide and iron oxide. , Carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate and other heat-resistant improvers, alumina, boron nitride, silicon carbide, metal powder and other heat conductivity-imparting agents, carbon black, silver powder, conductivity A conductivity-imparting agent such as carbon black can be added.
- reinforcing or semi-reinforcing fillers such as quartz powder, molten quartz powder, diatomaceous earth and calcium carbonate
- inorganic pigments such as titanium oxide, iron oxide, carbon black and cobalt aluminate, titanium oxide and iron oxide.
- an adhesion accelerator such as a carboxylic acid anhydride or a titanium acid ester, an adhesion imparting agent other than the component (D) and / or a silane coupling agent can be added.
- the above-mentioned components (A) to (D) and other optional components are mixed with a mixing device such as a planetary mixer, a loss mixer, a Hobart mixer, a kneader, a three-roll or the like, if necessary. It can be manufactured by uniformly mixing using the kneading device of.
- the method for producing the adhesive composition of the present invention is not particularly limited, and the adhesive composition can be produced by kneading the above components.
- the composition may be a two-agent composition and may be mixed at the time of use.
- the produced adhesive composition can be cured at room temperature depending on the type of the catalyst of the component (C), but it is often heated in order to accelerate the curing, and particularly good adhesiveness to various substrates. It is preferable to cure at 60 ° C. or higher, preferably 100 to 200 ° C. for several minutes to several hours in order to exhibit the above.
- the composition may be prepared with an appropriate fluorosolvent, for example, 1,3-bis (tri) within a range not affected by outgas during heat curing.
- fluoromethyl) benzene, Florinate (manufactured by 3M), perfluorobutylmethyl ether, perfluorobutylethyl ether and the like may be dissolved in a desired concentration before use.
- the adhesive composition of the present invention exhibits good adhesiveness to a wide variety of substrates such as metals and plastics.
- metals include aluminum, stainless steel (SUS), nickel, chromium, copper, zinc, and alloys of two or more of these
- plastics include epoxy resin, phenol resin, and PET (polyethylene terephthalate).
- Resin polyester resin such as PBT (polybutylene terephthalate) resin, PC (polycarbonate) resin, PPS (polyphenylene sulfide) resin, PA (polyamide) resin, PI (polyimide) resin, LCP (liquid crystal polymer) resin and the like. ..
- the thickness of the cured product of the adhesive composition of the present invention is preferably about 80 ⁇ m to 1 mm.
- the adhesive composition of the present invention is useful as an adhesive for various electric and electronic parts.
- It can be suitably used for a touch material or the like. More specifically, for example, it can be a die attach material for an in-vehicle sensor made of the adhesive composition of the present invention, and a protective sealant or coating agent for a printing / copying device made of the adhesive composition of the present invention. Can be done.
- the part indicates a mass part.
- the viscosity and adhesive strength show the measured values at 23 ° C. (Viscosity is measured according to the method by rotational viscosity of the viscosity test specified in JIS K6249, and the adhesive strength is JIS K6850 adhesive-rigid adherend. (Measured according to the tensile shear adhesive strength test method).
- the (number average) molecular weights of the compounds (58), (64), and (65) are polystyrene-equivalent number averages in gel permeation chromatography (GPC) analysis using AK-225 (manufactured by Asahi Glass Co., Ltd.) as a fluorosolvent as a developing solvent. It was calculated as the molecular weight.
- the (number average) molecular weight of the compounds (59), (60), (61), (63), (66) and (67) was obtained by performing 1 H-NMR measurement and 19 F-NMR measurement. It was calculated based on the integrated value of each unit in the compound calculated from the spectrum.
- the component (A1) is measured by infrared spectroscopy (IR) using a calibration curve, and the internal standard material is used for the components (A2), (A3) and (A4). It was measured by proton nuclear magnetic resonance spectroscopy ( 1 H-NMR). Further, the Si—H group amount of the component (B) ((B1), (B2), (B')) and the component D ((D1), (D2)) is the proton nuclear magnetic resonance using an internal standard material. It was measured by spectroscopy ( 1 H-NMR).
- the mass reduction rate of each of the following compounds when heated at 150 ° C. for 1 hour was determined by the following measuring method.
- a tare (W1) of a clean aluminum dish is weighed using a precision balance (reading limit 0.0001 mg), then 1.5 g of a sample (compound) is collected on the aluminum dish, and the sample is placed on the aluminum dish.
- the mass (W2) of (W2) is weighed using a precision balance, then the aluminum dish on which the sample is placed is left in a thermostat at 150 ° C. for 1 hour, and after heating, the aluminum dish is taken out from the thermostat and placed in a desiccator.
- Example 1 100 parts of the 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 weight 0.012 mol / 100 g), (C1).
- Me represents a methyl group.
- c' 8.
- i 9.
- Example 1 10 g of the adhesive composition of Example 1 and four sensor chips are placed adjacent to each other in a clean glass petri dish, and heated according to the above method (1 in an incubator at 150 ° C.). After leaving for hours) and allowing to cool (leave to cool in a desiccator for 3 hours), the sensor chip after this test was taken out and the degree of contamination of the gold pad was confirmed with a microscope. The results are shown in Table 1.
- Example 2 In Example 1, (E1) the compound represented by the following formula (62) was further added in an amount of 0.2 part to (A1) 100 parts of the polymer represented by the above formula (58). An adhesive composition was prepared in the same manner. The adhesive composition was subjected to the same contamination confirmation test and evaluation at the time of heat curing as in Example 1. The results are shown in Table 1.
- Example 3 100 parts of the polymer represented by the above formula (58) and 6.3 parts of fumed silica (Aerosil R-972 (trade name manufactured by Aerosil Co., Ltd.)) are kneaded at room temperature for 30 minutes using a planetary mixer. Further, the mixture was kneaded at 150 ° C. for 1 hour under a reduced pressure of ⁇ 98.0 kPaG.
- Example 4 In Example 3, (D2) a compound represented by the following formula (63) (number average molecular weight 1,024, Si—H group amount 0.098 mol / 100 g) is further represented by (A1) the above formula (58).
- An adhesive composition was prepared by the same method as in Example 3 except that 0.20 part was added to 100 parts of the polymer. The adhesive composition was subjected to the same contamination confirmation test and evaluation at the time of heat curing as in Example 1. The results are shown in Table 1. In the formula, Me represents a methyl group.
- Example 5 [Example 5] (A2) (C1) platinum in 100 parts of a polymer represented by the following formula (64) (number average molecular weight 6,450, mass reduction rate 0.4%, viscosity 60 mPa ⁇ s, vinyl group weight 0.031 mol / 100 g). -0.033 parts of an ethanol solution of the divinyltetramethyldisiloxane complex (platinum concentration 3.0% by mass), 0.25 parts of a 60% by mass toluene solution of ethynylcyclohexanol, (B1) the compound represented by the above formula (59).
- 614 number average molecular weight 6,450, mass reduction rate 0.4%, viscosity 60 mPa ⁇ s, vinyl group weight 0.031 mol / 100 g.
- -0.033 parts of an ethanol solution of the divinyltetramethyldisiloxane complex platinum concentration 3.0% by mass
- Example 6 In Example 3, instead of (A1) the polymer represented by the above formula (58), (A3) the polymer represented by the following formula (65) (number average molecular weight 15,630, mass reduction rate 0.4%, viscosity 11).
- Example 1 In Example 1, (B1) instead of the compound represented by the above formula (59), (B') the compound represented by the following formula (66) (number average molecular weight 762, mass reduction rate 100%, Si—H group weight) (0.394 mol / 100 g) was used in 1.83 parts, (B2) the compound represented by the above formula (60) was changed to 1.18 parts, and the adhesive composition was prepared in the same manner as in Example 1 except for the above. bottom. The adhesive composition was subjected to the same contamination confirmation test and evaluation at the time of heat curing as in Example 1. The results are shown in Table 1. In the formula, Me represents a methyl group.
- Example 2 In Example 1, instead of 100 parts of the polymer (A1) represented by the above formula (58), (A4) the polymer represented by the following formula (67) (number average molecular weight 1,810, mass reduction rate 28%, viscosity).
- FIG. 1 shows photographs of the appearance of the sensor chip before and after the contamination confirmation test during heat curing of Example 1.
- the circular pattern in the center of the photograph in FIG. 1 is the gold pad of the sensor chip.
- the sensor chip (FIG. 1 (b)) after the test showed no discoloration or poor appearance. ..
- FIG. 2 shows photographs of the appearance of the sensor chip before and after the contamination confirmation test during heat curing of Comparative Example 1.
- Comparative Example 1 the sensor chip (FIG. 2 (a)) in the state before the test (blank) is compared with the sensor chip (FIG. 2 (b)) after the test, and liquid or oil-like impurities adhere to the sensor chip and discolor. It was confirmed that As in Comparative Example 1, the gold pad contamination of the sensor chip was confirmed in Comparative Example 2.
- Adhesion test Two 100 mm x 25 mm test panels of various adherends (aluminum (Al), stainless steel (SUS), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS)) shown in Table 2 are 10 mm at each end.
- the compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 having a thickness of 1 mm are overlapped with each other so as to overlap each other, and the composition is cured by heating at 150 ° C. for 1 hour.
- Adhesion test pieces were prepared. Next, a tensile shear adhesion test (tensile speed 50 mm / min) was performed on these test pieces, and the adhesive strength (shear adhesive strength) and the cohesive fracture rate were evaluated. The results are shown in Table 2. In the table, the numerical value in the upper row is the shear adhesion strength, and the numerical value in parentheses in the lower row is the cohesive fracture rate (%).
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Abstract
Description
以上の理由から、パーフルオロポリエーテル系接着剤組成物においてベースポリマー以外の一部又は全ての成分は比較的低分子量であることが好ましく、かつ硬化時のアウトガスによる周囲部品の汚染が少ないパーフルオロポリエーテル系接着剤組成物が求められる。
〔1〕
(A)1分子中に少なくとも2個のアルケニル基を有し、かつ数平均分子量が2,000以上であり、(A)成分単独で150℃で1時間加熱したときの(A)成分の質量減少率が1%以下である直鎖状パーフルオロポリエーテル化合物: 100質量部、
(B)1分子中にケイ素原子に結合した水素原子を2個以上有し、かつ含フッ素有機基を1個以上有し、エポキシ基及びトリアルコキシシリル基を含まず、数平均分子量が1,000以上4,000以下であり、(B)成分単独で150℃で1時間加熱したときの(B)成分の質量減少率が20%以下である含フッ素オルガノ水素ポリシロキサン化合物: (A)成分中のアルケニル基1モルに対して(B)成分中のケイ素原子に結合した水素原子が0.1~2.5モルとなる量、
(C)白金族金属化合物: (A)成分の質量に対して白金族金属原子換算で0.1~1,000ppm、及び
(D)1分子中にケイ素原子に結合した水素原子と、炭素原子又は炭素原子と酸素原子を介してケイ素原子に結合したエポキシ基及び/又はトリアルコキシシリル基とをそれぞれ1個以上有し、数平均分子量が700以上のオルガノ水素ポリシロキサン化合物:(A)成分中のアルケニル基1モルに対して(D)成分中のケイ素原子に結合した水素原子が0.005~1.5モルとなる量
を含有してなる接着剤組成物。
〔2〕
(A)成分が下記一般式(1)で表される直鎖状パーフルオロポリエーテル化合物である〔1〕に記載の接着剤組成物。
Bは炭素原子又はケイ素原子であり、X1はそれぞれ独立し、少なくとも2個はアルケニル基であり、その他のX1は水素原子(Bが炭素原子の場合に限る)又はメチル基であり、Rf1は2価パーフルオロポリエーテル基である。]
〔3〕
(A)成分単独で150℃で1時間加熱したときの(A)成分の質量減少率が0.5%以下である〔1〕又は〔2〕に記載の接着剤組成物。
〔4〕
(A)成分のアルケニル含有量が、0.002~0.3mol/100gである請求項〔1〕~〔3〕のいずれかに記載の接着剤組成物。
〔5〕
(B)成分が、下記一般式(4)で表される含フッ素オルガノ水素ポリシロキサン化合物である〔1〕~〔4〕のいずれかに記載の接着剤組成物。
E-(C4F8О)c-(C3F6O)d-(C2F4O)e-(CF2O)f-CgF2g- (5)
(Eは、フッ素原子又は炭素数1~6のパーフルオロオキシアルキル基であり、c、d、e、fは、それぞれ独立して0~20の整数であり、2≦c+d+e+f≦20であり、gは1~3の整数である。上記( )の繰り返し単位はランダムに配列されていてよい。)]
〔6〕
(D)成分が、1分子中に窒素原子、炭素原子及び酸素原子から選ばれる少なくとも1種を含む2価の連結基を介してケイ素原子に結合した1価のパーフルオロアルキル基又は1価のパーフルオロオキシアルキル基を1個以上有するものである〔1〕~〔5〕のいずれかに記載の接着剤組成物。
〔7〕
更に、(E)カルボン酸無水物を(A)成分100質量部に対して0.010~10質量部含有する〔1〕~〔6〕のいずれかに記載の接着剤組成物。
〔8〕
〔1〕~〔7〕のいずれかに記載の接着剤組成物からなるダイアタッチ材。
〔9〕
車載センサー用である〔8〕に記載のダイアタッチ材。
〔10〕
〔1〕~〔7〕のいずれかに記載の接着剤組成物からなる保護用シール剤又はコーティング剤。
〔11〕
印刷・複写装置用又は燃料電池用である〔10〕に記載の保護用シール剤又はコーティング剤。
〔12〕
〔1〕~〔7〕のいずれかに記載の接着剤組成物の硬化物を有する電気・電子部品。
〔13〕
接着剤組成物の硬化物でセンサーチップを固定した車載センサー用物品である〔12〕に記載の電気・電子部品。
〔14〕
接着剤組成物の硬化物を保護用シール又はコーティング層とした印刷・複写装置用部品又は燃料電池用部品である〔12〕に記載の電気・電子部品。
[接着剤組成物]
本発明に係る接着剤組成物は、下記(A)、(B)、(C)及び(D)成分を含有してなることを特徴とするものである。
本発明の接着剤組成物に用いる(A)成分の直鎖状パーフルオロポリエーテル化合物は1分子中に少なくとも2個のアルケニル基を有し、かつ数平均分子量が2,000以上であり、(A)成分単独で150℃で1時間加熱したときの(A)成分の質量減少率が1%以下であるものであり、好ましくは後述する一般式(1)で示されるように主鎖中に2価のパーフルオロアルキルエーテル構造を有するものであって、本発明の接着剤組成物において主剤(ベースポリマー)として作用するものである。
なお、上記(A)成分としては、特開平9-95615号公報に記載の合成方法により得られる数平均分子量で2,000以上のものであり、特に4,000以上のものであることが望ましい。該数平均分子量が2,000未満の該直鎖状パーフルオロポリエーテル化合物は、加熱硬化時にそれ自身がアウトガスとして揮発する割合が大きくなり、周囲部品の汚染を引き起こすため好ましくない。なお、該数平均分子量の上限は、50,000以下、特には20,000以下程度であればよい。
この150℃加熱処理による(A)直鎖状パーフルオロポリエーテル化合物の質量減少率が1%(特には、1.0%)よりも大きい場合、これを含んだ接着剤組成物から加熱硬化時にアウトガスが発生して汚染を引き起こす。
{(W3-W1)/(W2-W1)}×100(単位:%)
W1:アルミ皿質量(g)
W2:アルミ皿質量+加熱前の試料質量(g)
W3:アルミ皿質量+加熱後の試料質量(g)
この質量減少率の測定方法は、後述する(B)、(D)成分においても同じである。
直鎖状パーフルオロポリエーテル化合物、好ましくは後述する一般式(1)で表される直鎖状パーフルオロポリエーテル化合物を1,330Pa以下、好ましくは665Pa以下の圧力下、100~300℃、好ましくは150~250℃の温度で、1時間以上、好ましくは5時間以上減圧処理することにより得る。
Bは炭素原子又はケイ素原子であり、X1はそれぞれ独立し、分子中に6個(分子鎖の両末端にそれぞれ3個ずつ)存在するX1のうち、少なくとも2個はアルケニル基であり、その他のX1は水素原子(Bが炭素原子の場合に限る)又はメチル基であり、Rf1は2価パーフルオロポリエーテル基である。]
また、分子中に6個(即ち、分子鎖両末端のそれぞれに3個ずつ)存在するX1のうち、少なくとも2個(特には、分子鎖両末端のそれぞれに3個ずつ存在するX1のうち、少なくとも1個ずつ)はアルケニル基であり、炭素数2~8、特に炭素数2~6で、かつ末端にCH2=CH-構造を有するものが好ましい。例えば、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等が挙げられ、中でもビニル基、アリル基が好ましい。X1は、アルケニル基でない場合、Bが炭素原子のときに水素原子又はメチル基のいずれかとなり、Bがケイ素原子のときにメチル基となった構造となる。
-(CaF2aO)x- (6)
(式(6)中、aは1~6の整数であり、xは5~600の整数、好ましくは10~400の整数、より好ましくは30~200の整数である。)
-CF2O-
-CF2CF2O-
-CF2CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2CF2O-
-CF2CF2CF2CF2CF2CF2O-
-CF2O-
-CF2CF2O-
-CF2CF2CF2O-
-CF(CF3)CF2O-
本発明の接着剤組成物に用いる(B)成分は、1分子中にケイ素原子に結合した水素原子(Si-H基)を2個以上有し、かつ含フッ素有機基を1個以上有し、エポキシ基及びトリアルコキシシリル基を含まず、数平均分子量が1,000以上4,000以下であり、(B)成分単独で150℃で1時間加熱したときの(B)成分の質量減少率が20%以下である含フッ素オルガノ水素ポリシロキサン化合物であり、(A)成分の架橋剤ないし鎖長延長剤として機能するものである。
E-(C4F8О)c-(C3F6O)d-(C2F4O)e-(CF2O)f-CgF2g- (5)
(Eは、フッ素原子又は炭素数1~6のパーフルオロオキシアルキル基であり、c、d、e、fは、それぞれ独立して0~20の整数であり、2≦c+d+e+f≦20であり、gは1~3の整数である。上記( )の繰り返し単位はランダムに配列されていてよい。)
(式中、R1は非置換又はハロゲン置換の1価炭化水素基であり、L1は上述した2価の連結基を介してケイ素原子に結合してもよい上記一般式(5)で表される1価のパーフルオロポリエーテル基である。w1は0~50の整数であり、好ましくは0~20の整数であり、x1は2~50の満たす整数であり、好ましくは3~20の整数であり、y1は1~50の整数であり、好ましくは1~20の整数である。また、w1+x1+y1は、上記に記したように数平均分子量1,000~4,000を満たすような整数であり、好ましくは3≦w1+x1+y1≦53であり、より好ましくは4≦w1+x1+y1≦20、更に好ましくは4≦w1+x1+y1≦10である。上記( )の繰り返し単位はランダムに配列されていてよい。)
上記(B)成分の配合量は、(A)成分を硬化する有効量であり、通常(A)成分中に含まれるビニル基、アリル基、シクロアルケニル基等のアルケニル基1モルに対し(B)成分中のヒドロシリル基、即ちSi-H基が0.1~2.5モル、好ましくは0.2~2モルとなる量である。ヒドロシリル基(≡Si-H基)が少なすぎると、架橋度合が不十分となる結果、硬化物が得られない場合があり、また、多すぎると硬化時に発泡してしまうことがある。
本発明の接着剤組成物に用いる(C)成分は、白金族金属化合物である。これはヒドロシリル化反応触媒であり、(A)成分中のアルケニル基と、(B)成分及び(D)成分中のヒドロシリル基との付加反応を促進する触媒である。このヒドロシリル化反応触媒は、一般に貴金属の化合物であり、高価格であることから、比較的入手し易い白金又は白金化合物がよく用いられる。
本発明の接着剤組成物に用いる(D)成分は、これを配合することによって本発明の組成物に自己接着性を十分に発現させるための接着性向上剤として作用するものであって、1分子中にケイ素原子に結合した水素原子(Si-H基)と、炭素原子又は炭素原子と酸素原子を介してケイ素原子に結合したエポキシ基及び/又はトリアルコキシシリル基とをそれぞれ1個以上有し、かつ数平均分子量が700以上であるオルガノ水素ポリシロキサン化合物である。
(D)成分のオルガノ水素ポリシロキサン化合物としては、下記一般式で表されるものを用いることができる。
-Z-Rf3 (44)
[式(44)中、Zはエーテル結合又はアミド結合を介していてもよい炭素数1~6の2価の有機基、下記一般式(45)で表される基及び一般式(46)で表される基から選ばれるいずれかの基であり、
Rf3は1価のパーフルオロポリエーテル基である。]
E1-(C4F8O)c1-(C3F6O)d1-(C2F4O)e1-(CF2O)f1-Cg1F2g1- (47)
(E1はフッ素原子又は炭素数1~6のパーフルオロオキシアルキル基であり、c1、d1、e1、f1はそれぞれ独立して0~20の整数であり、2≦c1+d1+e1+f1≦20となる。g1は1~3の整数である。上記( )の繰り返し単位はランダムに配列されていてよい。)
(式中、R4は炭素数1~10、特に炭素数1~4の2価炭化水素基(メチレン基、エチレン基、プロピレン基等のアルキレン基など)を示し、R5は独立に炭素数1~8、特に炭素数1~4の1価炭化水素基(メチル基、エチル基、プロピル基、ブチル基等のアルキル基など)を示す。)
(D)成分の配合量は、(A)成分中のアルケニル基1モルに対して(D)成分中のケイ素原子に結合した水素原子が0.005~1.5モルとなる量、好ましくは0.01~1.0モルとなる量、より好ましくは0.05~0.5モルとなる量である。(A)成分中のアルケニル基1モルに対して(D)成分中のケイ素原子に結合した水素原子が0.005モル未満の場合には十分な接着性が得られず、(A)成分中のアルケニル基1モルに対して(D)成分中のケイ素原子に結合した水素原子が1.5モルを超えると、組成物の流動性が悪くなり、得られる硬化物の物理的強度が低下し、また、硬化性を阻害することが多いので好ましくない。
(E)成分は、カルボン酸無水物であり、上記(D)成分の接着付与能力を向上させ、本発明の組成物を硬化して得られる硬化物の自己接着性発現を促進させるための任意成分である。該成分としては、エポキシ樹脂用の硬化剤として使用されているものを使用できる。
本発明の接着剤組成物においては、その実用性を高めるために上記の(A)~(E)成分以外にも、可塑剤、粘度調節剤、可撓性付与剤、ヒドロシリル化反応触媒の制御剤、無機質充填剤、接着促進剤、(D)成分以外の接着付加剤、シランカップリング剤等の各種配合剤を必要に応じて添加することができる。これら添加剤の配合量は、本発明の目的を損なわない範囲、及び組成物の特性及び硬化物の物性を損なわない限りにおいて任意である。
[式(57)中、X’は上記L2構造におけるZ(2価の連結基)と同じであり、p’は0又は1であり、Rf4は、下記一般式で表される1価のパーフルオロポリエーテル基である。
[式中、Y5は独立に式:Ck'F2k'+1-(k'は1~3の整数)で表される基であり、c2は1~200の整数であり、かつ上記一般式(1)で表される直鎖状パーフルオロポリエーテル化合物のRf1におけるzよりも小さい。]
(式中、Y6は上記Y5と同じであり、d2及びe2はそれぞれ1~200の整数であり、かつ、d2とe2の和は、上記一般式(1)で表される直鎖状パーフルオロポリエーテル化合物のRf1におけるn及びmの和よりも小さい。上記( )の繰り返し単位はランダムに配列されていてよい。)
CF3O-(CF2CF2CF2O)c2-CF2CF3
CF3-(OCF2CF2)e2(OCF2)d2-O-CF3
本発明の接着剤組成物は、上記した(A)~(D)成分とその他の任意成分とをプラネタリーミキサー、ロスミキサー、ホバートミキサー等の混合装置、必要に応じてニーダー、三本ロール等の混練装置を使用して均一に混合することによって製造することができる。
まず、清浄なアルミ皿の風袋(W1)を、精密天秤(読み取り限界0.0001mg)を用いて秤量し、次にアルミ皿に試料(化合物)を1.5g採取し、試料をのせたアルミ皿の質量(W2)を、精密天秤を用いて秤量し、次いで試料をのせたアルミ皿を150℃の恒温器の中に1時間放置し、加熱後、恒温器から該アルミ皿を取り出しデシケーター中で放冷し、放冷後、精密天秤を用いて試料をのせたアルミ皿の質量(W3)を秤量した。下式より、この試料の質量減少率を求めた。
{(W3-W1)/(W2-W1)}×100(単位:%)
W1:アルミ皿質量(g)
W2:アルミ皿質量+加熱前の試料質量(g)
W3:アルミ皿質量+加熱後の試料質量(g)
(A1)下記式(58)で示されるポリマー(数平均分子量15,550、質量減少率0.5%、粘度10,900mPa・s、ビニル基量0.012mol/100g)100部に、(C1)白金-ジビニルテトラメチルジシロキサン錯体のエタノール溶液(白金濃度3.0質量%)0.033部、エチニルシクロヘキサノールの60質量%トルエン溶液0.25部、(B1)下記式(59)で示される化合物(数平均分子量1,906、質量減少率7.0%、Si-H基量0.16mol/100g)3.00部、(B2)下記式(60)で示される化合物(数平均分子量1,720、質量減少率16.0%、Si-H基量0.52mol/100g)1.52部、(D1)下記式(61)で示される化合物(数平均分子量990、Si-H基量0.121mol/100g)2.00部を加え、混合して接着剤組成物を調製した。なお式中、Meはメチル基を示す。
次に、この組成物の加熱硬化時にアウトガスによる周囲汚染が発生するかどうかを確認するために、以下のような実験を行った。
センサーチップを4個用意し、顕微鏡を用いてセンサーチップ上の金パッドが汚染されていないことを確認した(試験前)。その後、清浄なガラスシャーレの中にセンサーチップを入れ、ガラスシャーレにふたをして、150℃の恒温器の中に1時間放置した。加熱後、恒温器からガラスシャーレを取り出し、デシケーター中で3時間放冷した。その後、ガラスシャーレからセンサーチップを取り出し、恒温器中に放置する前と同様、金パッドが汚染されていないことを顕微鏡により確認した。
次に、清浄なガラスシャーレの中に、実施例1の接着剤組成物10gと、センサーチップ4個とを互いに隣接するように配置し、上記方法に従って加熱(150℃の恒温器の中に1時間放置)及び放冷(デシケーター中で3時間放冷)後、この試験後のセンサーチップを取り出し顕微鏡により金パッドの汚染具合を確認した。その結果を表1に示す。
実施例1において、更に(E1)下記式(62)で示される化合物を、(A1)上記式(58)で示されるポリマー100部に対して0.2部加えたこと以外は実施例1と同様にして接着剤組成物を調製した。この接着剤組成物に関して、実施例1と同様の加熱硬化時の汚染確認試験及び評価を行った。その結果を表1に示す。
(A1)上記式(58)で示されるポリマー100部とヒュームドシリカ(Aerosil R-972(アエロジル社製商品名))6.3部を、プラネタリーミキサーを用いて室温で30分間混練し、さらに-98.0kPaGの減圧下、150℃で1時間混練した。混練物を室温まで冷却後、(C1)白金-ジビニルテトラメチルジシロキサン錯体のエタノール溶液(白金濃度3.0質量%)0.033部、エチニルシクロヘキサノールの60質量%トルエン溶液0.25部、(B1)上記式(59)で示される化合物3.00部、(B2)上記式(60)で示される化合物1.52部、(D1)上記式(61)で示される化合物2.00部、(E1)上記式(62)で示される化合物0.2部を加え、混合して接着剤組成物を調製した。この接着剤組成物に関して、実施例1と同様の加熱硬化時の汚染確認試験及び評価を行った。その結果を表1に示す。
実施例3において、更に(D2)下記式(63)で示される化合物(数平均分子量1,024、Si-H基量0.098mol/100g)を、(A1)上記式(58)で示されるポリマー100部に対して0.20部加え、それ以外は、全て実施例3と同様の方法により接着剤組成物を調製した。この接着剤組成物に関して、実施例1と同様の加熱硬化時の汚染確認試験及び評価を行った。その結果を表1に示す。なお式中、Meはメチル基を示す。
(A2)下記式(64)で示されるポリマー(数平均分子量6,450、質量減少率0.4%、粘度60mPa・s、ビニル基量0.031mol/100g)100部に、(C1)白金-ジビニルテトラメチルジシロキサン錯体のエタノール溶液(白金濃度3.0質量%)0.033部、エチニルシクロヘキサノールの60質量%トルエン溶液0.25部、(B1)上記式(59)で示される化合物19.4部、(B2)上記式(60)で示される化合物1.79部、(D1)上記式(61)で示される化合物2.0部、(E1)上記式(62)で示される化合物0.2部を加え、混合して接着剤組成物を調製した。この接着剤組成物に関して、実施例1と同様の加熱硬化時の汚染確認試験及び評価を行った。その結果を表1に示す。
実施例3において、(A1)上記式(58)で示されるポリマーの代わりに(A3)下記式(65)で示されるポリマー(数平均分子量15,630、質量減少率0.4%、粘度11,000mPa・s、ビニル基量0.012mol/100g)100部を用い、それ以外は実施例3と同様にして接着剤組成物を調製した。この接着剤組成物に関して、実施例1と同様の加熱硬化時の汚染確認試験及び評価を行った。その結果を表1に示す。なお式中、Meはメチル基を示す。
実施例1において、(B1)上記式(59)で示される化合物の代わりに(B’)下記式(66)で示される化合物(数平均分子量762、質量減少率100%、Si-H基量0.394mol/100g)を1.83部用い、(B2)上記式(60)で示される化合物を1.18部に変更し、それ以外は実施例1と同様にして接着剤組成物を調製した。この接着剤組成物に関して、実施例1と同様の加熱硬化時の汚染確認試験及び評価を行った。その結果を表1に示す。なお式中、Meはメチル基を示す。
実施例1において、上記式(58)で示されるポリマー(A1)100部の代わりに、(A4)下記式(67)で示されるポリマー(数平均分子量1,810、質量減少率28%、粘度28mPa・s、ビニル基量0.10mol/100g)100部を用いたこと以外は実施例1と同様にして接着剤組成物を調製した。この接着剤組成物に関して、実施例1と同様の加熱硬化時の汚染確認試験及び評価を行った。
表2に記載の各種被着体(アルミニウム(Al)、ステンレス鋼(SUS)、ポリブチレンテレフタレート(PBT)、ポリフェニレンサルファイド(PPS))の100mm×25mmのテストパネル2枚をそれぞれの端部が10mmずつ重複するように、厚さ1mmの上記実施例1~6及び比較例1,2で得た各組成物の層を挟んで重ね合わせ、150℃で1時間加熱することにより該組成物を硬化させ接着試験片を作製した。次いで、これらの試験片について引張剪断接着試験(引張速度50mm/分)を行い、接着強度(剪断接着強さ)及び凝集破壊率を評価した。それらの結果を表2に示す。表中、上の段の数値が剪断接着強さであり、下の段のカッコ内の数値が凝集破壊率(%)である。
Claims (14)
- (A)1分子中に少なくとも2個のアルケニル基を有し、かつ数平均分子量が2,000以上であり、(A)成分単独で150℃で1時間加熱したときの(A)成分の質量減少率が1%以下である直鎖状パーフルオロポリエーテル化合物: 100質量部、
(B)1分子中にケイ素原子に結合した水素原子を2個以上有し、かつ含フッ素有機基を1個以上有し、エポキシ基及びトリアルコキシシリル基を含まず、数平均分子量が1,000以上4,000以下であり、(B)成分単独で150℃で1時間加熱したときの(B)成分の質量減少率が20%以下である含フッ素オルガノ水素ポリシロキサン化合物: (A)成分中のアルケニル基1モルに対して(B)成分中のケイ素原子に結合した水素原子が0.1~2.5モルとなる量、
(C)白金族金属化合物: (A)成分の質量に対して白金族金属原子換算で0.1~1,000ppm、及び
(D)1分子中にケイ素原子に結合した水素原子と、炭素原子又は炭素原子と酸素原子を介してケイ素原子に結合したエポキシ基及び/又はトリアルコキシシリル基とをそれぞれ1個以上有し、数平均分子量が700以上のオルガノ水素ポリシロキサン化合物:(A)成分中のアルケニル基1モルに対して(D)成分中のケイ素原子に結合した水素原子が0.005~1.5モルとなる量
を含有してなる接着剤組成物。 - (A)成分が下記一般式(1)で表される直鎖状パーフルオロポリエーテル化合物である請求項1に記載の接着剤組成物。
Bは炭素原子又はケイ素原子であり、X1はそれぞれ独立し、少なくとも2個はアルケニル基であり、その他のX1は水素原子(Bが炭素原子の場合に限る)又はメチル基であり、Rf1は2価パーフルオロポリエーテル基である。] - (A)成分単独で150℃で1時間加熱したときの(A)成分の質量減少率が0.5%以下である請求項1又は2に記載の接着剤組成物。
- (A)成分のアルケニル含有量が、0.002~0.3mol/100gである請求項1~3のいずれか1項に記載の接着剤組成物。
- (B)成分が、下記一般式(4)で表される含フッ素オルガノ水素ポリシロキサン化合物である請求項1~4のいずれか1項に記載の接着剤組成物。
E-(C4F8О)c-(C3F6O)d-(C2F4O)e-(CF2O)f-CgF2g- (5)
(Eは、フッ素原子又は炭素数1~6のパーフルオロオキシアルキル基であり、c、d、e、fは、それぞれ独立して0~20の整数であり、2≦c+d+e+f≦20であり、gは1~3の整数である。上記( )の繰り返し単位はランダムに配列されていてよい。)] - (D)成分が、1分子中に窒素原子、炭素原子及び酸素原子から選ばれる少なくとも1種を含む2価の連結基を介してケイ素原子に結合した1価のパーフルオロアルキル基又は1価のパーフルオロオキシアルキル基を1個以上有するものである請求項1~5のいずれか1項に記載の接着剤組成物。
- 更に、(E)カルボン酸無水物を(A)成分100質量部に対して0.010~10質量部含有する請求項1~6のいずれか1項に記載の接着剤組成物。
- 請求項1~7のいずれか1項に記載の接着剤組成物からなるダイアタッチ材。
- 車載センサー用である請求項8に記載のダイアタッチ材。
- 請求項1~7のいずれか1項に記載の接着剤組成物からなる保護用シール剤又はコーティング剤。
- 印刷・複写装置用又は燃料電池用である請求項10に記載の保護用シール剤又はコーティング剤。
- 請求項1~7のいずれか1項に記載の接着剤組成物の硬化物を有する電気・電子部品。
- 接着剤組成物の硬化物でセンサーチップを固定した車載センサー用物品である請求項12に記載の電気・電子部品。
- 接着剤組成物の硬化物を保護用シール又はコーティング層とした印刷・複写装置用部品又は燃料電池用部品である請求項12に記載の電気・電子部品。
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JPH0995615A (ja) | 1995-09-29 | 1997-04-08 | Shin Etsu Chem Co Ltd | 硬化性組成物 |
JP2005126618A (ja) * | 2003-10-27 | 2005-05-19 | Shin Etsu Chem Co Ltd | 低汚染性接着剤組成物 |
JP2018123206A (ja) * | 2017-01-30 | 2018-08-09 | 信越化学工業株式会社 | 含フッ素コーティング剤組成物及びコーティングされた物品 |
JP2019006969A (ja) * | 2017-06-26 | 2019-01-17 | 信越化学工業株式会社 | 熱硬化性フルオロポリエーテル系接着剤組成物及び電気・電子部品 |
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JPH0995615A (ja) | 1995-09-29 | 1997-04-08 | Shin Etsu Chem Co Ltd | 硬化性組成物 |
JP2005126618A (ja) * | 2003-10-27 | 2005-05-19 | Shin Etsu Chem Co Ltd | 低汚染性接着剤組成物 |
JP4582287B2 (ja) | 2003-10-27 | 2010-11-17 | 信越化学工業株式会社 | 低汚染性接着剤組成物 |
JP2018123206A (ja) * | 2017-01-30 | 2018-08-09 | 信越化学工業株式会社 | 含フッ素コーティング剤組成物及びコーティングされた物品 |
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