Classifications

• • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
• • 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
• • 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
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
  • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • 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
  • C09J2483/00—Presence of polysiloxane
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

• the present invention relates to a cured organopolysiloxane film characterized by having few surface and internal defects and having excellent dielectric breakdown strength, its use, and its production method.
• the cured organopolysiloxane having a polysiloxane skeleton is excellent in transparency, electric insulation, heat resistance, cold resistance, etc., and improves electric activity by introducing a high dielectric functional group such as a fluoroalkyl group as required. Since it can be easily processed into a film or sheet, it can be used for various applications, including adhesive films used for various electric and electronic devices and electroactive films used for transducer devices such as actuators. These organopolysiloxane cured products are classified into a hydrosilylation reaction curing type, a condensation reaction curing type, a peroxide curing type, and the like, depending on the curing mechanism.
• a cured product of an organopolysiloxane using a curable organopolysiloxane composition of a hydrosilylation reaction-curable type is widely used because it is rapidly cured by leaving at room temperature or heating and does not generate by-products.
• a cured organopolysiloxane film is a thin film having a thickness of 100 ⁇ m or less in addition to a high degree of uniformity. Moldability tends to be required. However, when the cured organopolysiloxane is molded into a thin film, defects may occur on the surface and inside of the film due to minute voids (voids) and dust floating in the air.
• Patent Document 1 a provision of a highly dielectric film excellent in uniformity and flatness in the width direction of the film, and a use and a production method thereof.
• the film is effective in realizing a cured organopolysiloxane film having excellent flatness by suppressing the variation and unevenness of the thickness, but it still improves microscopic defects on the film surface or inside the film. Leave room for.
• the present invention has been made in order to solve the above-mentioned problems, and it is possible to make the film thinner, the number of defects on the surface and inside of the film is extremely small, and the cured organopolysiloxane film exhibits a high dielectric breakdown strength with respect to a charged voltage. , Its use and its manufacturing method.
• the present inventors have found that the number of defects on the film surface per unit area, preferably the number of defects inside the film per unit area is suppressed to a certain value or less.
• the present inventors have found that the above-mentioned problems can be solved by a cured organopolysiloxane film having an average thickness in the range of 1 to 200 ⁇ m, and have reached the present invention.
• the object of the present invention is: [1] A cured organopolysiloxane film having an average thickness in the range of 1 to 200 ⁇ m, and a surface defect of the cured film using optical means within a range of 15 mm ⁇ 15 mm as a unit area at an arbitrary portion of the film.
• the object of the present invention is achieved by the following cured organopolysiloxane film.
• [3] The cured organopolysiloxane film according to [1] or [2], wherein the dielectric breakdown strength measured at room temperature is in the range of 60 V / ⁇ m to 200 V / ⁇ m.
• [4] The cured organopolysiloxane film according to any one of [1] to [3], which is substantially transparent and has an average thickness of 1 to 150 ⁇ m.
• the object of the invention is solved by a film obtained by rolling or a film which has been flattened by curing between separators provided with a release layer.
• the cured organopolysiloxane film is preferably obtained by curing a curable organopolysiloxane composition curable by a hydrosilylation reaction. That is, the object of the present invention is achieved by the following cured organopolysiloxane film.
• [5] The cured organopolysiloxane film according to any one of [1] to [4], which is rolled.
• the organopolysiloxane cured film according to the object of the present invention is used as an electroactive film (for example, a dielectric film) used for a transducer such as an actuator, a highly dielectric functional group is introduced into the cured product.
• a highly dielectric functional group is introduced into the cured product.
• the object of the present invention is achieved by the following cured organopolysiloxane film.
• a part or all of the component (A) or the component (B) has (C p F 2p + 1 ) -R- (R is an alkylene group having 1 to 10 carbon atoms in the molecule, and p is 1
• An object of the present invention is a use of the above-mentioned cured organopolysiloxane film, a laminate provided with the film, and a use thereof, and is achieved by the following invention.
• [11] Use of the cured organopolysiloxane film according to any one of [1] to [10] as an electronic material or a member for a display device.
• [12] A laminate having a structure in which the cured organopolysiloxane film according to any one of [1] to [10] is laminated on a sheet-like substrate provided with a release layer.
• An electronic component or a display device having the cured organopolysiloxane film according to any one of [1] to [10].
• the object of the present invention is achieved by the invention of the method for producing a cured organopolysiloxane film.
• membrane which can be made into a thin film, the number of defects on the surface and inside of the film is extremely small, and shows a high dielectric strength against a charged voltage, and its use and a production method are provided.
• the cured organopolysiloxane film is excellent in various properties expected from silicone materials such as handling workability and transparency and heat resistance, and is a film or sheet-like member suitable as an adhesive layer or a dielectric layer of electronic parts and the like. , Gel, elastomer, optical bonding and the like.
• the cured organopolysiloxane film is a film or a sheet-like member which is thinner and has excellent dielectric breakdown strength under high voltage, electronic materials, electronic members for display devices such as touch panels, and transducers such as actuators. It can be suitably used for use as a material.
• organopolysiloxane cured product film of the present invention will be described in detail.
• the cured organopolysiloxane film of the present invention is in the form of a thin film, and has an average thickness of 1 to 200 ⁇ m, preferably an average thickness of 1 to 150 ⁇ m, and an average thickness of 1 to 150 ⁇ m. More preferably, it is in the range of 100100 ⁇ m.
• the average thickness of the film is an average value of the thickness at the center of the film.
• the cured organopolysiloxane film is uniform and flat, the difference between the thickness at the end and the thickness at the center is within 5.0% in the width direction of the film, and the average thickness at the center of the film is average.
• the width direction of the film is a direction perpendicular to the length direction of the film, and is generally a direction perpendicular to the plane direction with respect to the direction in which the curable organopolysiloxane composition as a raw material is applied on the substrate.
• the winding direction is the length direction
• the width direction of the film is a direction perpendicular to the length direction.
• the width direction of the film is a direction perpendicular to the long axis direction, and in the case of a square or substantially square film, either the direction perpendicular or parallel to each side of the square film May be the width direction.
• the difference (absolute value) between the terminal thickness ( ⁇ m) and the center thickness ( ⁇ m) in the width direction of the film is within 5.0% and within 4.0%. Is preferable, and it is particularly preferable that it is within 3.5%.
• the film is preferably a flat and uniform structure having substantially no unevenness on the surface including the bulges at both ends, and the maximum displacement (difference) of the thickness in the film width direction is 5.0% or less. It is particularly preferable that the film has a maximum displacement (difference) in thickness of 5.0% or less in the entire film and is a flat film having substantially no unevenness. In particular, when the film is flat, not only a single layer but also a plurality of film layers are superimposed to form a uniform thick film layer. It has the advantage of being difficult.
• the cured organopolysiloxane film of the present invention has an average thickness per sheet in the range of 1 to 200 ⁇ m. However, a plurality of films are stacked to form a laminated film exceeding 200 ⁇ m, and an adhesive layer or a dielectric film is formed. It can be used for the purpose of forming a layer. In particular, a dielectric film constituting a dielectric layer formed by laminating two or more such films is included in the scope of the present invention.
• the cured organopolysiloxane film of the present invention preferably has a fixed size (area), a film width of 30 mm or more, and a film area of 900 mm 2 or more.
• a film is, for example, an organopolysiloxane cured film of 30 mm square or more.
• the cured organopolysiloxane film of the present invention may have a structure in which the curable composition of the raw material is uniformly applied and cured even on the release layer. Even if the length can be wound on a roll, it can be used without limitation. Needless to say, the cured organopolysiloxane film may be cut into a desired size and shape before use.
• the cured organopolysiloxane film of the present invention is characterized in that defects on the surface of the film are extremely small at any part of the film.
• a defect on the film surface is a contaminated site on the film surface due to adhesion of voids, dust, floating dust, and the like derived from air bubbles. Since a visual defect is generated, particularly when a high voltage is applied to the film and a current is applied, the film may cause dielectric breakdown of the film at the site. Note that surface defects, particularly minute voids having a diameter of several to several tens ⁇ m, may be difficult to visually confirm.
• the cured organopolysiloxane film of the present invention is obtained by measuring the number of surface defects using optical means in an arbitrary area of the film within a range of 15 mm ⁇ 15 mm as a unit area.
• the number of surface defects is in the range of 0 to 1, preferably in the range of 0 to 0.5, and more preferably in the range of 0 to 0.1.
• the measurement of the number of defects using optical means means that light is emitted from a light source having a constant illuminance to the surface at a fixed incident angle, and the reflected light is detected by an optical means such as a CCD camera.
• a signal having a certain signal threshold is counted as a surface defect.
• the illuminance at the film position becomes constant at a specific incident angle (for example, 10 to 60 degrees) from a white LED light source installed at a certain distance (for example, 50 to 300 mm) from the film.
• the specularly reflected light (reflected light having a reflection angle corresponding to the above-mentioned incident angle) is set at a position at a fixed distance from the film (for example, 50 to 400 mm).
• the scanning speed is 10 m / min. Is detected by a CCD camera having a pixel size of 10 ⁇ m, the detected signal is differentiated in the scanning direction, the number of defects having a specific signal threshold is counted over the entire film roll, and the film is 15 mm ⁇ 15 mm. Can be converted into the number of defects per range having a unit area.
• the organopolysiloxane cured product is used.
• the number of defects on the film surface can be specified by irradiating the film with light from a white LED light source having a constant surface incident angle and detecting the reflected light.
• the cured organopolysiloxane film of the present invention is in the form of a thin film, it is preferable that the number of defects inside the film is also suppressed. Specifically, when the number of internal defects is measured using an optical means within a range of 15 mm ⁇ 15 mm as a unit area at an arbitrary portion of the film, the number of internal defects is in a range of 0 to 20. And the range of 0 to 15 is preferable. When the number of internal defects exceeds the above upper limit, when a high voltage is applied to the film and current is applied, dielectric breakdown easily occurs, and the dielectric breakdown strength of the entire film is significantly reduced.
• the number of internal defects can be specified by measuring the number of defects using optical means.
• a light source having a constant illuminance irradiates light perpendicular to the lower surface of the film, and detects the transmitted light with an optical means such as a CCD camera to obtain a constant signal threshold.
• an optical means such as a CCD camera
• the organopolysiloxane cured product is used.
• MaxEye.Impact a line camera having a line speed of 10 ⁇ m / min, a width resolution of 0.01 mm / pixel, and a flow resolution of 0.01 mm / scan
• the organopolysiloxane cured product is used.
• the number of defects inside the film can be specified.
• the cured organopolysiloxane film of the present invention is substantially transparent when not containing a colorant or a filler having a large particle diameter, and is used as a dielectric layer or an adhesive layer in applications requiring transparency / visibility. Can be used.
• substantially transparent means that when a film-shaped cured product having an average thickness of 1 to 200 ⁇ m is formed, it is visually transparent. In general, the transmittance of light having a wavelength of 450 nm is reduced. It is 80% or more when the value of air is 100%.
• a suitable cured organopolysiloxane film is thin and highly transparent, preferably has an average thickness in the range of 1 to 150 ⁇ m, more preferably has an average thickness in the range of 1 to 100 ⁇ m, Those having a light transmittance of 90% or more are particularly preferable.
• dielectric breakdown strength is a measure of the dielectric breakdown resistance of the present film under an applied DC or AC voltage, and the applied voltage before dielectric breakdown is divided by the thickness of the present film. Thereby, a dielectric breakdown strength value or a dielectric breakdown voltage value is obtained.
• the dielectric breakdown strength in the present invention is measured in a unit of a potential difference with respect to a unit of a film thickness (in the present invention, volt / micrometer (V / ⁇ m)).
• a dielectric breakdown strength can be measured by an electric insulating oil breakdown voltage tester (for example, Portatest 100A-2 manufactured by Soken Co., Ltd.) having a program based on a standard such as JIS 2101-82.
• the dielectric breakdown strength is measured at least at any position on the film at least 10 points, and the standard deviation value is sufficiently small. Is preferred.
• the cured organopolysiloxane film of the present invention may have a dielectric breakdown strength measured at room temperature in the range of 60 V / ⁇ m to 200 V / ⁇ m, and in the range of 70 V / ⁇ m to 100 V / ⁇ m. More preferred. When the number of defects on the film surface and inside exceeds the upper limit, the dielectric breakdown strength described above may not be realized. Furthermore, since the organopolysiloxane cured film of the present invention is entirely uniform and contains almost no microscopic defects, the standard deviation value of the dielectric breakdown strength is sufficiently small, and 0.1 to 10.0 V / ⁇ m. And preferably in the range of 0.1 to 5.0 V / ⁇ m.
• the cured organopolysiloxane film of the present invention may optionally introduce a high dielectric functional group such as a fluoroalkyl group, and the relative dielectric constant of the whole film at 1 kHz and 25 ° C. is easily designed to be 3 or more. be able to.
• the relative dielectric constant can be designed by the introduction amount of the high dielectric functional group and the use of the high dielectric filler, etc., and compared with the cured organopolysiloxane film having a relative dielectric constant of 4 or more, 5 or more, or 6 or more. Can be easily obtained.
• the cured organopolysiloxane film of the present invention is characterized in that it has few microscopic surface and internal defects, and macroscopic mechanical properties such as hardness, tear strength, and tensile strength have the same chemical composition.
• the organopolysiloxane cured film designed with the film thickness and shape.
• the cured organopolysiloxane can be designed to have the following mechanical properties measured based on JIS K 6249 when heat-formed into a 2.0 mm thick sheet.
• the Young's modulus (MPa) can be set to 10 MPa or less at room temperature, and a particularly preferable range is 0.1 to 2.5 MPa.
• the tear strength (N / mm) at room temperature can be 1 N / mm or more, and a particularly preferable range is 2 N / mm or more.
• the tensile strength (MPa) can be 1 MPa or more at room temperature, and a particularly preferable range is 2 MPa or more.
• the elongation at break (%) can be 200% or more, and a particularly preferable range is 200-1000%.
• the shear storage modulus at 23 ° C. is 10 3 to 10. It is preferably in the range of 5 Pa, more preferably in the range of 1.0 ⁇ 10 3 to 5.0 ⁇ 10 4 Pa.
• the residual compression set (%) of the cured organopolysiloxane film is preferably less than 10%, more preferably less than 5%, and particularly preferably 4% or less.
• a material having a residual compression set (%) of less than 3% can be designed.
• the cured product of the organopolysiloxane film of the present invention preferably has a compression ratio (%) of 15% or more, more preferably 18% or more, and particularly preferably 20% or more.
• the cured organopolysiloxane film of the present invention When used as an adhesive or an adhesive layer, it may be designed to have a desired adhesive strength by using an organopolysiloxane resin or the like.
• a test piece obtained by laminating a polyethylene terephthalate (PET) base material (thickness: 50 ⁇ m) on both sides of a cured organopolysiloxane film having a thickness of 100 ⁇ m is performed in an environment of 23 ° C. and 50% humidity, at a speed of 300 mm / min.
• PET polyethylene terephthalate
• the adhesive strength can be designed to be 5 N / m or more, or 10 N / m or more.
• the substrate itself to which the organopolysiloxane cured product film of the present invention adheres can be provided with an adhesive force based on various treatments or is not used as an adhesive layer, there is substantially no adhesive force, It goes without saying that an easily peelable organopolysiloxane cured film can be used.
• the cured organopolysiloxane of the present invention is obtained by curing the curable organopolysiloxane composition so as to have the above thickness.
• the curing reaction mechanism is not particularly limited, for example, a hydrosilylation reaction curing type using an alkenyl group and a silicon-bonded hydrogen atom; a dehydration condensation reaction curing type using a silanol group and / or a silicon-bonded alkoxy group, and dealcoholation Condensation reaction curing type; peroxide curing reaction type using organic peroxide; and radical reaction curing type by irradiating high-energy rays to mercapto groups, etc., and the whole is cured relatively quickly to facilitate the reaction.
• hydrosilylation reaction curing type a peroxide curing reaction type, a radical reaction curing type, and a combination thereof. These curing reactions proceed upon heating, irradiation with high energy rays, or a combination thereof.
• a hydrosilylation-curable curable organopolysiloxane composition in the present invention, since a cured product of the organopolysiloxane having extremely few defects on the film surface and inside is obtained by the production method described below. .
• a cured organopolysiloxane film obtained by curing a curable organopolysiloxane composition, wherein the component (A) is (A1) a linear or branched organopolysiloxane having an alkenyl group only at the molecular chain terminal, and (A2) an alkenyl group-containing organopolysiloxane resin having at least one branched siloxane unit in the molecule and having a vinyl (CH2 CH—) group content in the range of 1.0 to 5.0% by mass; More preferably, the organopolysiloxane mixture is contained.
• the component (A) is an organopolysiloxane having a curing reactive group containing a carbon-carbon double bond, and is a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group.
• An alkenyl group having 2 to 20 carbon atoms such as a benzyl group, a decenyl group, an undecenyl group or a dodecenyl group; an acryl-containing group such as a 3-acryloxypropyl group or a 4-acryloxybutyl group; a 3-methacryloxypropyl group or a 4-methacrylic group
• a linear, branched, cyclic, or resinous (network) organopolysiloxane containing a curing reactive group selected from methacryl-containing groups such as a roxybutyl group in the molecule is exemplified.
• an organopolysiloxane having a curing reactive group containing a carbon-carbon double bond selected from a vinyl group, an allyl group or a hexenyl group is preferred.
• the organopolysiloxane as the component (A) may contain a group selected from a monovalent hydrocarbon group having no carbon-carbon double bond in the molecule, a hydroxyl group and an alkoxy group. Further, in the monovalent hydrocarbon group, a part of the hydrogen atoms may be substituted with a halogen atom or a hydroxyl group. Examples of such monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like.
• Alkyl group such as phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group and pyrenyl group; benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group, phenane
• Aralkyl groups such as tolylethyl group and pyrenylethyl group
• hydrogen atoms of these aryl groups or aralkyl groups are alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group; And a group substituted with a halogen atom.
• component (A) contains a hydroxyl group or the like, the component has condensation reactivity in addition to hydrosilylation reaction curability.
• component (A) has the following average composition formula: R 1 a R 2 b SiO (4-ab) / 2 Or a mixture thereof.
• R 1 is a curing reactive group containing a carbon-carbon double bond as described above
• R 2 is a group selected from the above-mentioned monovalent hydrocarbon groups having no carbon-carbon double bond, hydroxyl groups and alkoxy groups
• a and b are numbers satisfying the following conditions: 1 ⁇ a + b ⁇ 3 and 0.001 ⁇ a / (a + b) ⁇ 0.33, preferably, the following conditions: 1.5 ⁇ a + b ⁇ 2.5 and It is a number that satisfies 0.005 ⁇ a / (a + b) ⁇ 0.2.
• Component (a1) has, at its molecular chain end (Alk) R 2 2 SiO 1/2 (Wherein, Alk is an alkenyl group having 2 or more carbon atoms) having a siloxane unit represented by other siloxane units consist substantially only siloxane units represented by R 2 2 SiO 2/2 straight It is a linear or branched organopolysiloxane.
• R 2 represents the same group as described above.
• the siloxane polymerization degree of the component (A1-1), including terminal siloxane units, is in the range of 7 to 1002, and may be in the range of 102 to 902.
• Such component (A1-1) is particularly preferably both ends of the molecular chain (Alk) blocked with a siloxane unit represented by R 2 2 SiO 1/2, in linear organopolysiloxanes is there.
• Component (a2) is an alkenyl group-containing organopolysiloxane resin, Average unit formula: (RSiO 3/2 ) o (R 2 SiO 2/2 ) p (R 3 SiO 1/2 ) q (SiO 4/2 ) r (XO 1/2 ) s
• the alkenyl group-containing organopolysiloxane resin represented by the following formula is exemplified.
• R is a group selected from an alkenyl group and the aforementioned monovalent hydrocarbon group having no carbon-carbon double bond
• X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• R is an alkenyl group.
• R on the siloxane unit represented by RSiO 1/2 is an alkenyl group.
• (o + r) is a positive number
• p is 0 or a positive number
• q is 0 or a positive number
• s is 0 or a positive number
• p / (o + r) is 0 to Q / (o + r) is a number in the range of 0 to 5
• (o + r) / (o + p + q + r) is a number in the range of 0.3 to 0.9
• s / (O + p + q + r) is a number in the range of 0 to 0.4.
• component (a2) particularly preferably, ⁇ (Alk) R 2 2 SiO 1/2 ⁇ q1 (R 2 3 SiO 1/2) q2 (SiO 4/2) r
• q1 + q2 + r is a number in the range of 50 to 500
• (q1 + q2) / r is a number in the range of 0.1 to 2.0
• q2 is (The content of the vinyl (CH 2 CHCH—) group in the organopolysiloxane resin is a number that satisfies the range of 1.0 to 5.0% by mass.)
• An alkenyl group-containing MQ organopolysiloxane resin represented by the following formula is exemplified.
• the composition as a whole has excellent curability, and It can provide a cured product excellent in mechanical strength and flexibility, and can provide a cured organopolysiloxane film particularly suited to the adhesive layer or the dielectric layer in the above-mentioned electronic parts and the like.
• Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule, and functions as a crosslinking agent for component (A).
• 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogen) (Siloxy) phenylsilane, molecular hydrogen-terminated trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain-terminated trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain-terminal dimethylhydrogensiloxy group-blocked dimethylpoly Siloxane, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer with both molecular chains at both ends, methylhydrogensiloxane / diphenylsiloxane copolymer with trimethylsiloxy group at both molecular chains
• Component (B) is used in an amount of 0.1 to 10 moles of silicon-bonded hydrogen atoms, preferably 1 mole of carbon-carbon double bond in component (A) in the composition.
• the amount is preferably in the range of 0.1 to 5.0 mol, and particularly preferably in the range of 0.1 to 2.5 mol. If the amount of the component (B) is less than the lower limit, it may cause poor curing. If the content of the component (B) exceeds the upper limit, the mechanical strength of the cured product becomes too high, and the adhesive layer or In some cases, physical properties suitable for the dielectric layer cannot be obtained.
• Component (C) is a catalyst that promotes the hydrosilylation reaction of components (A) and (B), and includes a platinum-based catalyst, a rhodium-based catalyst, a palladium-based catalyst, a nickel-based catalyst, an iridium-based catalyst, a ruthenium-based catalyst, and An iron-based catalyst is exemplified, and a platinum-based catalyst is preferable.
• the platinum-based catalyst include platinum-based compounds such as platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, and alkenylsiloxane complexes of platinum.
• the alkenyl siloxane includes 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which a part of the methyl groups of these alkenyl siloxanes are substituted with an ethyl group, a phenyl group, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with an allyl group, a hexenyl group, and the like.
• 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable because the platinum-alkenylsiloxane complex has good stability. Further, since the stability of the platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1 1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1 It is preferable to add an alkenyl siloxane such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as a dimethyl siloxane oligomer, and particularly, to add an alken
• the amount of component (C) used is an effective amount and is not particularly limited, but is not particularly limited as long as it promotes the curing of the curable organopolysiloxane composition of the present invention. Specifically, based on the sum of the components (A) to (C) (totaling 100% by mass), the metal atoms in the catalyst are 0.01 to 1,000 ppm by mass, preferably ( The amount is such that the amount of platinum metal atoms in the component (C) falls within the range of 0.1 to 500 ppm.
• the curing When the content of the component (C) is less than the lower limit of the above range, the curing may be insufficient, and when the content of the component (C) exceeds the upper limit of the above range, it is uneconomical and the obtained cured product may be colored. May adversely affect transparency.
• the curable organopolysiloxane composition according to the present invention can be subjected to a curing reaction as it is.
• the composition or a part of its components for example, an organopolysiloxane resin
• an organic solvent can be used as necessary to improve its miscibility and handleability.
• the viscosity may be adjusted using a solvent so that the total viscosity becomes 100 to 50,000 mPa ⁇ s.
• the solvent (D) may be 0 parts by mass, which is preferable.
• the curable organopolysiloxane composition of the present invention can be designed to be solvent-free by selecting a polymer having a low degree of polymerization, and a fluorine-containing solvent, an organic solvent, or the like can be contained in a cured film. Is not left, and there is an advantage that the problem of environmental load and the influence of the solvent on the electronic device can be eliminated.
• the type of the organic solvent used herein is not particularly limited as long as it is a compound capable of dissolving all or some of the components in the composition, and those having a boiling point of 80 ° C. or more and less than 200 ° C. It is preferably used.
• the amount of the organic solvent used here is preferably in the range of 0 to 2,000 parts by mass, assuming that the sum of the components (A) to (C) is 100 parts by mass, and is preferably 5 to 500 parts by mass, 10 to 300 parts by mass. Parts by mass are more preferred.
• the amount of the organic solvent is substantially 0 parts by mass, and it is preferable that the organic solvent is free from the solvent, depending on the use of the cured film of the present invention.
• the viscosity at 25 ° C. of the curable organopolysiloxane composition according to the present invention is not particularly limited, but is preferably in the range of 100 to 500,000 mPa ⁇ s, more preferably 300 to 100,000 mPa ⁇ s, and particularly preferably. Is in the range of 1,000 to 10,000 mPa ⁇ s. It is also possible to adjust the amount of the organic solvent used for the purpose of setting the viscosity in a preferable range.
• the introduction of a highly dielectric functional group can be achieved by using an organopolysiloxane or organohydrogenpolysiloxane having a highly dielectric functional group as a part or all of the component (A) or the component (B). It can be carried out by adding an organic additive having a functional group, a non-reactive organic silicon compound having a highly dielectric functional group, or the like to the curable composition. From the viewpoint of improving the miscibility in the curable composition and the relative dielectric constant of the cured product, the organopolysiloxane or the organohydrogenpolysiloxane as the component (A) or the component (B) may contain all the components on the silicon atom. It is preferable that at least 10 mol%, preferably at least 20 mol%, more preferably at least 40 mol% of the substituents are substituted with a highly dielectric functional group.
• the type of the highly dielectric functional group introduced into the cured organopolysiloxane film is not particularly limited, but a) a halogen atom represented by a 3,3,3-trifluoropropyl group or the like; Containing group, b) nitrogen atom-containing group represented by cyanopropyl group, etc., c) oxygen atom-containing group represented by carbonyl group, etc., d) heterocyclic group such as imidazole group, e) boron such as borate ester group.
• Examples include a containing group, f) a phosphorus-containing group such as a phosphine group, and g) a sulfur-containing group such as a thiol group.
• a halogen atom containing a fluorine atom and a halogen atom-containing group are preferably used.
• the high dielectric functional group is (C p F 2p + 1 ) -R- (R is an alkylene group having 1 to 10 carbon atoms. , P is an integer of 1 or more and 8 or less).
• R is an alkylene group having 1 to 10 carbon atoms.
• P is an integer of 1 or more and 8 or less.
• a fluoroalkyl group examples include a trifluoropropyl group, a pentafluorobutyl group, a heptafluoropentyl group, a nonafluorohexyl group, an undecafluoroheptyl group, a tridecafluorooctyl group, a pentadecafluorononyl group, Heptadecafluorodecyl group.
• the curable organopolysiloxane composition according to the present invention may contain components other than the above components, if necessary, as long as the object of the present invention is not impaired.
• the other components include a hydrosilylation reaction inhibitor, a release agent, an insulating additive, an adhesion improver, a heat resistance improver, a filler, a pigment and other conventionally known various additives.
• an inorganic filler can be blended for the purpose of adjusting the overall viscosity and improving functionality such as improvement in dielectric properties.
• the hydrosilylation reaction inhibitor is compounded to suppress the cross-linking reaction occurring between the component (A) and the component (B), extend the pot life at room temperature, and improve the storage stability. is there. Therefore, the curable composition of the present invention is a component that is inevitably blended in practical use.
• hydrosilylation reaction inhibitor examples include acetylene compounds, eneyne compounds, organic nitrogen compounds, organic phosphorus compounds and oxime compounds. Specifically, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 1-ethynyl-1-cyclo Alkyne alcohols such as hexanol and phenylbutynol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-1-hexyn-3-yne; 1,3,5,7-tetramethyl Methylalkenylcyclosiloxanes such as 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; benzotriazole is exemplified Is done.
• the compounding amount of the hydrosilylation reaction inhibitor is an amount effective for extending the pot life at room temperature and improving the storage stability according to the present invention. Usually, it is in the range of 0.001 to 5% by mass, and preferably in the range of 0.01 to 2% by mass per 100% by mass of the component (A). It may be appropriately selected according to the content, the amount of alkenyl groups in component (A), the amount of silicon-bonded hydrogen atoms in component (B), and the like.
• a filler may or may not be used as desired.
• a filler one or both of an inorganic filler and an organic filler can be used.
• the type of the filler used is not particularly limited, and examples thereof include a highly dielectric filler, a conductive filler, an insulating filler, and a reinforcing filler, and one or more of these can be used.
• the composition of the present invention within the range that does not impair its transparency, coating properties and handling workability, for the purpose of adjusting viscosity or imparting functionality, a high dielectric filler, a conductive filler, One or more fillers selected from the group consisting of insulating fillers and reinforcing fillers can be contained.
• a filler selected from the group consisting of insulating fillers and reinforcing fillers.
• at least one or more reinforcing fillers are used. It is preferable to mix them.
• some or all of the filler may be surface-treated with one or more surface treatment agents.
• the filler may be one type or two or more types, and the shape is not particularly limited, and any shape such as a particle shape, a plate shape, a needle shape, and a fiber shape can be used. .
• the shape of the filler is particles
• the particle diameter of the filler is not particularly limited.
• the volume average particle diameter is, for example, 0.001. It can be in the range of up to 500 ⁇ m.
• the volume average particle diameter of the filler can be 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, 10 ⁇ m or less, or 0.01 ⁇ m or more, 0.1 ⁇ m or more, and 1 ⁇ m or more.
• the filler may have an aspect ratio of 1.5 or more, 5 or more, or 10 or more.
• fine particles having a volume average particle diameter of 0.01 ⁇ m or less and a maximum particle diameter of 0.02 ⁇ m or less are used, a substantially transparent cured product, particularly, an adhesive film or an electroactive film is produced. May be able to.
• preferred fillers are one or more types of reinforcing inorganic fine particles having an average primary particle diameter of less than 50 nm from the viewpoint of the mechanical strength of the cured product, and include fumed silica, wet silica, pulverized silica, and carbonic acid. Examples include calcium, diatomaceous earth, finely ground quartz, various metal oxide powders other than alumina and zinc oxide, glass fibers, carbon fibers, and the like. Further, these may be treated with various surface treatment agents described below. Among them, silica is recommended.
• the hydrophilic or hydrophilic resin having an average primary particle diameter of 10 nm or less, partially aggregated, and having a specific surface area of 50 m 2 / g or more and 300 m 2 / g or less.
• Hydrophobic fumed silica is treated with silazane or a silane coupling agent described later.
• One of these reinforcing inorganic particles may be used alone, or two or more thereof may be used in combination.
• the mechanical strength and dielectric breakdown of a cured organopolysiloxane obtained by curing the curable organopolysiloxane composition according to the present invention by incorporating reinforcing inorganic fine particles into the composition. It is possible to increase the strength.
• the compounding amount of these reinforcing inorganic fine particles is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.1 to 10% by mass, based on the curable organopolysiloxane composition. If the amount is out of the preferred range described above, the effect of mixing the inorganic particles may not be obtained, or the moldability of the curable organopolysiloxane composition may be reduced.
• a part or all of the inorganic fine particles (regardless of particle diameter, function, etc.) used in the curable organopolysiloxane composition according to the present invention may be surface-treated with one or more surface treatment agents.
• the type of the surface treatment is not particularly limited, and includes a hydrophilization treatment or a hydrophobization treatment, but a hydrophobization treatment is preferable.
• the hydrophobic fine particles When used, they can be dispersed at a high filling rate in the organopolysiloxane composition. In addition, an increase in the viscosity of the composition is suppressed, and the moldability is improved.
• the surface treatment can be performed by treating (or coating) the inorganic fine particles with a surface treating agent.
• the surface treatment agent for hydrophobization include at least one surface treatment agent selected from the group consisting of an organic titanium compound, an organic silicon compound, an organic zirconium compound, an organic aluminum compound, and an organic phosphorus compound.
• the surface treatment agents may be used alone or in combination of two or more.
• organosilicon compounds among them, silazanes, silanes, siloxanes, and polysiloxanes are preferred, and silazanes, alkyltrialkoxysilanes, and one-terminal trialkoxyxylpolydimethylsiloxanes are most preferably used. Is done.
• the ratio of the surface treatment agent to the total amount of the inorganic fine particles is preferably in a range of 0.1% by mass or more and 10% by mass or less, more preferably in a range of 0.3% by mass or more and 5% by mass or less.
• the treatment amount is the ratio of the inorganic particles to the surface treatment agent, and it is preferable to remove excess treatment agent after the treatment.
• Other functional fillers include dielectric inorganic fine particles, conductive inorganic fine particles, insulating inorganic fine particles, and heat conductive inorganic fine particles. One or more selected from these fine particles can be used in the composition of the present invention. In addition, these inorganic fine particles may have two or more types of functions such as a function as a reinforcing filler.
• Examples of preferable dielectric inorganic fine particles include titanium oxide, barium titanate, strontium titanate, lead zirconate titanate, and a part of barium and titanium parts of barium titanate, calcium, strontium, yttrium, neodymium, samarium, dysprosium.
• One or more inorganic fine particles selected from the group consisting of a composite metal oxide substituted with an alkaline earth metal, zirconium, or a rare earth metal such as titanium oxide, barium titanate, barium calcium zirconate titanate, And strontium titanate are more preferred, and titanium oxide and barium titanate are still more preferred.
• the dielectric inorganic fine particles have a relative dielectric constant of 10 or more at room temperature and 1 kHz.
• the upper limit of the preferred size (average primary particle size) of the inorganic fine particles is 20,000 nm (20 ⁇ m), but in consideration of the processability of a thin film for a transducer described later, the upper limit is 10,000 nm (10 ⁇ m). More preferred.
• the use of the dielectric inorganic fine particles can further improve the mechanical properties and / or electrical properties, particularly the relative dielectric constant of the cured organopolysiloxane.
• the conductive inorganic fine particles are not particularly limited as long as they can impart conductivity to the cured organopolysiloxane.
• conductive carbon such as conductive carbon black, graphite, and vapor grown carbon (VGCF); and metal powders such as platinum, gold, silver, copper, nickel, tin, zinc, iron, and aluminum;
• the conductive inorganic fine particles are glass fibers, silica alumina fibers, alumina fibers, fibers such as carbon fibers, as well as needle-like reinforcing materials such as aluminum borate whiskers, potassium titanate whiskers, glass beads, talc, mica,
• An inorganic filler such as graphite, wollastonite, dolomite or the like may be coated with a conductive material such as metal on the surface.
• the insulating inorganic fine particles usable in the present invention are not limited as long as they are generally known insulating inorganic materials, that is, particles of an inorganic material having a volume resistivity of 10 10 to 10 18 ⁇ ⁇ cm. , Flakes, and fibers (including whiskers). Specific examples include ceramic spherical particles, plate-like particles, and fibers, and alumina, iron oxide, copper oxide, metal silicates such as mica and talc, quartz, amorphous silica, and particles such as glass are preferably used. As an example. Further, these may be treated with various surface treatment agents described below. These can be used alone or in combination of two or more. By blending the insulating inorganic fine particles in the composition, the mechanical strength and dielectric breakdown strength of the cured organopolysiloxane can be increased, and the relative dielectric constant may be increased in some cases.
• the amount of the insulating inorganic particles is preferably in the range of 0.1 to 20% by mass, more preferably 0.1 to 5% by mass, based on the curable organopolysiloxane composition, depending on the use. If the compounding amount is outside the above preferred range, the effect of the compounding may not be obtained, or the mechanical strength of the cured organopolysiloxane may decrease.
• thermally conductive inorganic fine particles usable in the present invention include metal oxide particles such as magnesium oxide, zinc oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, silver oxide, and aluminum nitride, boron nitride, and silicon carbide. And inorganic compound particles such as silicon nitride, boron carbide, titanium carbide, diamond, and diamond-like carbon. Zinc oxide, boron nitride, silicon carbide, and silicon nitride are preferred. By incorporating one or more of these heat conductive inorganic fine particles into the composition, it becomes possible to increase the heat conductivity of the cured organopolysiloxane.
• metal oxide particles such as magnesium oxide, zinc oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, silver oxide, and aluminum nitride, boron nitride, and silicon carbide.
• inorganic compound particles such as silicon nitride, boron carbide, titanium carbide, diamond, and diamond-like carbon
• the measurement of the average particle diameter of these inorganic particles can be performed by a usual measurement method in the art. For example, when the average particle diameter is 50 nm or more and about 500 nm or less, a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a scanning electron microscope (SEM), and a field emission scanning electron
• TEM transmission electron microscope
• FE-TEM field emission transmission electron microscope
• SEM scanning electron microscope
• the average primary particle diameter can be measured by measuring the particle diameter by microscopic observation such as a microscope (FE-SEM) and determining the average value.
• the average particle diameter is about 500 nm or more
• the value of the average primary particle diameter can be directly obtained by a laser diffraction / scattering type particle size distribution analyzer or the like.
• the curable organopolysiloxane composition according to the present invention may further contain an additive for improving the releasability or dielectric breakdown characteristics, an adhesion improver, and the like.
• the cured film or sheet obtained by curing the curable organopolysiloxane composition according to the present invention into a thin film can be used as an adhesive film, an electroactive film (dielectric layer or electrode layer) constituting a transducer.
• an adhesive film an electroactive film (dielectric layer or electrode layer) constituting a transducer.
• the film may be damaged due to mold release, particularly when an organopolysiloxane cured film is produced at a high speed. .
• a dielectric layer used for an actuator, a touch panel, or the like is required to have reduced adhesiveness in order to improve sensitivity under low pressure.
• the curable organopolysiloxane composition according to the present invention can improve the production speed of the film without damaging the film, and can further reduce the tackiness by adding other release agents. is there.
• release-enhancing additive applicable to the curable organopolysiloxane composition according to the present invention
• the dielectric breakdown property improver is preferably an electric insulation improver, and a hydroxide or salt of aluminum or magnesium, a clay mineral, and a mixture thereof, specifically, aluminum silicate, aluminum sulfate, water It can be selected from the group consisting of aluminum oxide, magnesium hydroxide, calcined clay, montmorillonite, hydrotalcite, talc, and mixtures thereof.
• the insulating property improver may be treated by a known surface treatment method. These specific examples are the same as those proposed in the above-mentioned International Patent Publication WO2014 / 105959, for example.
• the adhesion improver is for improving the adhesion to the substrate with which the curable organopolysiloxane composition of the present invention is in contact during curing. It is an effective additive when the cured dielectric layer of the composition is not removed again.
• Organic adhesive alkoxysilane compounds such as vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and siloxanes thereof Derivatives, particularly chain or three-dimensional resin-like siloxane derivatives substituted with a fluorine-containing organic group are exemplified.
• (G1) a reaction mixture of an amino group-containing organoalkoxysilane and an epoxy group-containing organoalkoxysilane (g2) having at least two alkoxysilyl groups in one molecule, and between the silyl groups other than a silicon-oxygen bond
• An organic compound containing a bond of (G3) General formula: R a n Si (OR b) 4-n (Wherein R a is a monovalent epoxy group-containing organic group, R b is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and n is a number in the range of 1 to 3)
• R a is a monovalent epoxy group-containing organic group
• R b is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom
• n is a number in the range of 1 to 3
• alkoxysilanes excluding those having an epoxy group-containing organic group
• partial hydrolyzed condensates thereof Is exemplified.
• phenol-based, quinone-based, amine-based, phosphorus-based, phosphite-based, sulfur-based, thioether-based antioxidants; triazole-based, benzophenone-based, etc. as long as the technical effects of the present invention are not impaired.
• At least one kind of anti-static agent consisting of phosphoric acid ester type, halogen type, phosphorus type, antimony type etc .; cationic surfactant, anionic surfactant, nonionic surfactant etc. Agents; dyes, pigments and the like.
• the curable organopolysiloxane composition of the present invention is obtained by uniformly mixing the curable organopolysiloxane and a curing reaction accelerating component, preferably the above components (A) to (C), and if necessary. It can be prepared by adding other optional components and mixing uniformly. Mixing may be performed at room temperature by using various stirrers or kneaders. However, any combination of components that do not cure during mixing may be mixed under heating.
• the order of blending the components is not particularly limited as long as the components are not cured during mixing.
• the crosslinking agent for example, component (B)
• the curing reaction promoting component for example, component (C)
• the components in all the containers may be mixed immediately before use.
• the curing reaction of the curable organopolysiloxane composition of the present invention proceeds at room temperature in a curing reaction based on a condensation reaction such as dehydration and dealcoholation, but produces an organopolysiloxane cured product film by an industrial production process. In this case, it is usually achieved by heating the composition or exposing the composition to active energy rays.
• the curing reaction temperature by heat is not particularly limited, but is preferably from 50 ° C to 200 ° C, more preferably from 60 ° C to 200 ° C, and even more preferably from 80 ° C to 180 ° C.
• the time required for the curing reaction depends on the structure of the above components (A), (B) and (C), but is usually 1 second or more and 3 hours or less. In general, a cured product can be obtained by holding at 90 to 180 ° C. for 10 seconds to 30 minutes. In addition, the manufacturing method of a film, rolling, etc. are mentioned later.
• Examples of the active energy ray that can be used for the curing reaction include ultraviolet rays, electron beams, and radiation, but ultraviolet rays are preferred from the viewpoint of practicality.
• a hydrosilylation reaction catalyst having a high activity against ultraviolet rays to be used for example, a bis (2,4-pentanedionato) platinum complex, a (methylcyclopentadienyl) trimethylplatinum complex, Is desirably added.
• the ultraviolet light source a high-pressure mercury lamp, a medium-pressure mercury lamp, a Xe-Hg lamp, a deep UV lamp, and the like are suitable, and the irradiation amount at that time is preferably 100 to 8,000 mJ / cm 2 .
• the cured organopolysiloxane film of the present invention is a high-precision functional film containing almost no minute defects on its surface and inside, and is a flat film macroscopically having substantially no irregularities.
• Such a cured organopolysiloxane film is preferably produced in a clean room in order to avoid the adhesion of airborne dust and the like to the surface and inside.
• the cured organopolysiloxane film of the present invention can be suitably obtained by curing the above-mentioned curable organopolysiloxane composition while sandwiching it between separators having a release layer.
• the cured organopolysiloxane film of the present invention can be suitably realized by applying the above-described curable organopolysiloxane composition into a film, and curing the film by heating or the like after rolling.
• the cured organopolysiloxane film of the present invention itself may be further rolled, or the film coated or cured between separators provided with a release layer may be further rolled.
• their structures and manufacturing methods will be described.
• the cured organopolysiloxane film according to the present invention is obtained by converting the curable organopolysiloxane composition into a film-like substrate, a tape-like substrate, or a sheet-like substrate (hereinafter, referred to as a “film-like substrate”). After coating, the composition can be cured by a method corresponding to the curing mechanism to form the composition on the surface of the substrate.
• the substrate is particularly a planar substrate having a release surface, and the curable organopolysiloxane composition is preferably applied on the release surface. Since such a base material functions as a separator, the cured organopolysiloxane film of the present invention laminated on the base material is smoothly separated from the release layer by a slight force and adheres to a target electronic device or the like. In addition, since they can be adhered to each other, they have an advantage of being excellent in handling workability.
• Examples of the type of the substrate include paperboard, corrugated paper, clay-coated paper, polyolefin-laminated paper, especially polyethylene-laminated paper, synthetic resin film / sheet, natural fiber cloth, synthetic fiber cloth, artificial leather cloth, and metal foil.
• a synthetic resin film or sheet is preferable, and examples of the synthetic resin include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and nylon.
• a film of a heat-resistant synthetic resin such as polyimide, polyetheretherketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide, or polyethersulfone is suitable.
• a heat-resistant synthetic resin such as polyimide, polyetheretherketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide, or polyethersulfone.
• transparent substrates specifically, transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN are preferred.
• the substrate is preferably in the form of a film or a sheet.
• the thickness is not particularly limited, but is usually about 5 to 300 ⁇ m.
• a support film subjected to a primer treatment, a corona treatment, an etching treatment, and a plasma treatment may be used.
• the surface of the film-shaped substrate opposite to the surface of the pressure-sensitive adhesive layer may be subjected to a surface treatment such as a treatment such as scratch prevention, stain prevention, fingerprint adhesion prevention, glare prevention, reflection prevention, and antistatic treatment. .
• the method of applying the curable organopolysiloxane composition to give the cured organopolysiloxane film of the present invention to a substrate includes gravure coating, offset coating, offset gravure, roll coating using an offset transfer roll coater, and the like.
• a roll coat, an air knife coat, a curtain coat using a curtain flow coater, a comma coat, a Meyer bar, and other known methods for forming a cured layer can be used without limitation.
• the cured organopolysiloxane film of the present invention is an adhesive layer (including a pressure-sensitive adhesive layer) or an electroactive film (including a dielectric film such as a dielectric layer), the cured layer has a release coating ability. It is preferable to handle as a laminate film laminated on a film substrate having a release layer in a peelable state.
• the high dielectric film of the present invention is obtained by applying the curable organopolysiloxane composition on a substrate and then performing rolling before or after the curing reaction.
• the rolling process can be performed on the cured or semi-cured organopolysiloxane cured product, but after rolling the uncured curable organopolysiloxane composition, it is cured by heating or the like to obtain a flat and uniform material. It is preferred to obtain a cured organopolysiloxane film.
• the entire laminate obtained by applying the uncured curable organopolysiloxane composition between separators having a release layer described below is rolled, and then cured by heating or the like to obtain a flat and uniform layer. It is particularly preferred to obtain a cured organopolysiloxane film.
• the amount of the curable organopolysiloxane composition to be applied on the substrate must be such that the cured film has an average thickness of 1 to 200 ⁇ m and can be rolled.
• Rolling can be performed by applying a curable organopolysiloxane composition onto a substrate and using a known rolling method such as roll rolling. After the cured organopolysiloxane in a cured or semi-cured state is formed into a substantially sheet shape as necessary, rolling may be performed.
• the cured organopolysiloxane film after the rolling process needs to have an average thickness of 1 to 200 ⁇ m.
• an organopolysiloxane cured product film having a desired thickness can be designed by adjusting the gap between the rolls. For example, when the average thickness is in the range of 1 to 200 ⁇ m, the roll thickness can be reduced.
• the gap between the rolls is adjusted in the range of 2.0 to 4.0 times the average thickness of the target cured organopolysiloxane film.
• the thickness of the release layer is particularly preferably in the range of 100 to 200 ⁇ m. If the gap is larger than the upper limit, in particular, voids derived from bubbles may not be sufficiently eliminated, and defects on the film surface and inside may increase.
• the rolling process is preferably performed in a state in which the curable organopolysiloxane composition is applied on a substrate and is in an uncured state.
• the curable organopolysiloxane composition as a raw material is preferably applied onto a sheet-like substrate provided with a release layer, and is rolled by roll rolling or the like, and then flattened.
• the siloxane composition can be cured by heating or the like to obtain the cured organopolysiloxane film of the present invention.
• the method of applying the curable organopolysiloxane composition to the substrate before the rolling process, the substrate and the like are the same as described above, and for the fluoroalkyl group-containing organopolysiloxane having the primer layer and the flattening layer, Further, rolling processing such as roll rolling may be performed.
• a substrate having a release layer is applied to the coated surface of the above-mentioned curable organopolysiloxane composition, and the uncured coated surface is applied to each substrate (separator).
• the flattening layer a laminate obtained by applying an uncured curable organopolysiloxane composition between separators having a release layer is formed using a known rolling method such as the above-described roll rolling. Rolling is preferred.
• the thickness of the release layer on the separator is in the range of 0.1 to 1.5 times the average thickness of the target cured organopolysiloxane film.
• the thickness of the release layer is particularly preferably in the range of 5 to 75 ⁇ m.
• organopolysiloxane cured film Since the organopolysiloxane cured product film of the present invention has very few minute defects (voids (voids) due to air bubbles, contaminated sites by dust or floating dust) on the film surface and inside the film, a high voltage is applied to the film. When a voltage is applied and energized, dielectric breakdown due to the defect hardly occurs, high dielectric strength can be realized as a whole film, and adhesiveness / adhesiveness can be realized as desired in addition to transparency and flatness.
• voids voids due to air bubbles, contaminated sites by dust or floating dust
• the cured organopolysiloxane film of the present invention is useful as an electronic material, a member for a display device or a member for a transducer (including a sensor, a speaker, an actuator, and a generator). It can be suitably used as an adhesive film or an electroactive film (including a highly dielectric film) as a component of an electronic component or a display device.
• a transparent adhesive film or an electroactive film is suitable as a display panel or a member for a display, and is particularly useful for a so-called touch panel application that can operate a device, particularly an electronic device by touching a screen with a fingertip or the like. is there.
• an electroactive film having a high dielectric breakdown strength is suitable for a transducer member such as an actuator in the form of a single layer or a laminated film, and is particularly useful for an actuator used under a high voltage.
• organopolysiloxane cured film of the present invention is not limited at all except for the ones disclosed above, and may be a television receiver, a monitor for a computer, a monitor for a portable information terminal, a monitor for monitoring, a video camera, a digital camera, a portable camera.
• FPDs flat panel displays
• the device examples include a display device such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface electrolytic display (SED), a field emission display (FED), and a touch panel using these devices.
• a display device such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface electrolytic display (SED), a field emission display (FED), and a touch panel using these devices.
• SED surface electrolytic display
• FED field emission display
• the cured organopolysiloxane film of the present invention is a film-like or sheet-like member having excellent electrical and mechanical properties including dielectric breakdown strength, and optionally has a high relative dielectric constant and mechanical strength. (Specifically, tensile strength, tear strength, elongation, etc.).
• the cured organopolysiloxane film can be used as an electronic material, a member for a display device, or a member for a transducer (including for a sensor, a speaker, an actuator, and a generator). It can be suitably used as a film (dielectric layer or electrode layer).
• a known method of using a dielectric layer or a pressure-sensitive adhesive layer can be used without any particular limitation.
• Component (a1) Blocking of a vinyldimethylsiloxy group at both terminals, dimethylsiloxane polymer (vinyl group content (mass%) is 0.09, siloxane polymerization degree is 835)
• component (a3): CH 2 CH (CH 3) vinyl dimethylsiloxy units (M Vi units) represented by 2 SiO 0.5, (CH 3) 3 trimethylsiloxy units (M units) represented by SiO 0.5 and ,
• Example 1 As liquid curable organopolysiloxane composition 1, 66.48% by weight of component (a1), 15.41% by weight of component (a2), 5.08% by weight of component (a3), 2.46% by weight of component (b), Component (c) was blended and prepared so that 0.21% by weight, component (d) was 9.18% by weight, and component (e) was 1.18% by weight. At that time, the amount of the silicon-bonded hydrogen atom (Si—H) of the component (b) was about 1.6 mol per 1 mol of the vinyl group in the composition.
• Si—H silicon-bonded hydrogen atom
• Example 2 As a liquid curable organopolysiloxane composition, 65.44% by weight of the component (a4), 2.63% by weight of the component (a5), 5.21% by weight of the component (b2), 5.21% by weight of the component (b3), 0.10% by weight of (c), 18.80% by weight of component (d2), 2.33% by weight of component (d3), and 0.28% by weight of component (f) were prepared. At that time, the amount used was such that the silicon-bonded hydrogen atom (Si—H) of the component (b) was about 1.2 mol per 1 mol of the vinyl group in the composition.
• Si—H silicon-bonded hydrogen atom
• the light projection distance and the light reception distance were the same as in the internal defect measurement, and the light projection angle and the light reception angle were each set to 60 °.
• the base level was set to 256 for both the internal defect and the surface defect, the threshold value was set to 35 for the internal defect, and the surface defect was set to 40.
• the number of in-plane 15 mm ⁇ 15 mm defects of the film produced above is shown below.
• both films are derived from the same curable organopolysiloxane composition and also have an average thickness of 50 ⁇ m (common), the improvement in their electrical properties and the like can be achieved by reducing the number of defects on the film surface and inside in Examples. It is thought to be due to
• the cured organopolysiloxane film 2 having a dielectric functional group according to Example 2 had a very small number of defects on the film surface and inside, and had a small dielectric breakdown strength and a small variation. Therefore, it is considered that the number of defects on the surface and inside of the film greatly affects the electrical properties and the like even for the cured organopolysiloxane film having a dielectric functional group.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=69163716

Family Applications (1)

Country Status (7)

Cited By (3)

Families Citing this family (3)

Citations (4)

Family Cites Families (9)

• 2019
  • 2019-07-16 EP EP19837333.4A patent/EP3825352A4/en active Pending
  • 2019-07-16 JP JP2020531304A patent/JP7376479B2/ja active Active
  • 2019-07-16 CN CN201980054220.3A patent/CN112673056A/zh active Pending
  • 2019-07-16 KR KR1020217004691A patent/KR102802701B1/ko active Active
  • 2019-07-16 WO PCT/JP2019/027836 patent/WO2020017480A1/ja not_active Ceased
  • 2019-07-16 US US17/260,118 patent/US11725081B2/en active Active
  • 2019-07-17 TW TW108125195A patent/TWI823971B/zh active

Patent Citations (4)

Also Published As

Similar Documents

Legal Events