Classifications

• • 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
• • 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
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
• • 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
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3227—Compounds containing acyclic nitrogen atoms
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • 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
  • C08J2400/00—Characterised by the use of unspecified polymers
  • C08J2400/22—Thermoplastic resins
• • 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
  • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
  • C08J2463/02—Polyglycidyl ethers of bis-phenols
• • 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
  • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
  • C08J2481/06—Polysulfones; Polyethersulfones

Definitions

• the present invention relates to a resin film with a release sheet that contains large particles.
• resin films with release sheets obtained by thinly spreading resin have been widely used in electronic parts, automobiles, adhesives, medical parts, etc., taking advantage of their ease of handling and processability.
• resin films resin films with release sheets obtained by thinly spreading resin
• Patent Document 1 describes adhesive films for semiconductors, and proposes to specify the surface energy of the substrate to which the resin is applied in order to provide a resin film that combines good thin film coating properties and easy peeling properties and suppresses pinholes and repelling, and specifies the film thickness as 10 ⁇ m or less, while also describing the use of particulate fillers, with a maximum particle size of 25 ⁇ m or less.
• fillers when fillers are present in a resin film, fillers containing volatile components are prone to voids, swelling and peeling, making it difficult to coat the resin uniformly and with good quality.
• fillers with a particle size smaller than the resin thickness are generally blended, but when resin films are laminated for the purpose of imparting functionality such as thermal conductivity, particulate fillers with a particle size larger than the resin thickness may be blended.
• particulate fillers with a large particle size are blended, pinholes and repellency are likely to occur with the filler as the base point when or after the resin is placed on the release sheet, resulting in a problem of deterioration in the quality of the resin film.
• Patent Document 2 proposes specifying the B/C ratio (ratio of B roll (coating roll) speed to C roll (back roll) speed) using a reverse roll coater method in order to provide a high-quality resin film containing coarse particles with a particle size larger than the resin thickness.
• a resin containing particles with a particle diameter larger than the thickness of the resin is used as the particles to be contained in the resin film, not only does the above-mentioned repelling occur when the resin is placed on one side of the release sheet, but the repelling becomes greater over time, and the quality of the resin film tends to deteriorate. Therefore, it is necessary to increase the viscosity of the resin to suppress fluidity or change the surface properties of the release sheet to make it easier to hold the resin. However, if the viscosity of the resin is increased to make it easier to hold on the release sheet, the peelability of the resin from the release sheet becomes poor.
• Patent Document 1 achieves both good thin film coating properties and peelability from the substrate, and although it is described that a particulate filler with a maximum diameter exceeding twice the film thickness can be used, a composition containing particles with a maximum diameter within twice the film thickness is considered to be a more preferable embodiment, and no specific problems that arise when particles with a particle diameter sufficiently large relative to the film thickness are used, and no solutions to these problems have been found.
• Patent Document 2 discloses the use of particles containing coarse particles exceeding 2A ⁇ m for the resin thickness A ⁇ m of the resin film. However, Patent Document 2 does not mention or suggest the problem of the above-mentioned repellency that may occur due to coarse particles.
• Patent Document 2 states that in the composition that produces a high-quality resin film, the amount of particles containing coarse particles used is small, and the content of the coarse particles is 2 mass% or less for one of the two types of particles used. It can be said that there is an instruction to avoid a composition with a sufficiently high content of coarse particles, but does not disclose any technology necessary to obtain a high-quality resin film using a resin that contains coarse particles in excess of the amount described above in the composition.
• the prior art documents did not recognize the problem of repellency that occurs specifically when the resin film contains particles with a diameter larger than the thickness of the resin film, and did not specifically disclose methods for suppressing this problem. As a result, it was difficult to obtain a resin film that suppresses the spread of repellency, has good quality, and is easily peelable from the release sheet.
• the problem that the present invention aims to solve is to provide a resin film that is of good quality with good peelability from the release sheet, with the spread of repellency suppressed, even though a resin containing particles with a particle size sufficiently large relative to the thickness of the resin film is placed on one side of the release sheet.
• the present invention for solving the above problems has the following configuration:
• particles having a particle diameter exceeding twice the average resin thickness A of the resin composition arranged on one side of a release sheet i.e., particles having a particle diameter exceeding 2A (2 ⁇ A)
• large particle diameter particles are referred to as large particle diameter particles.
• a resin film with a release sheet in which a resin composition containing the following components [A] to [D] is disposed on one side of the release sheet, The particles [D] are contained in the resin composition in an amount of 10 to 30% by mass,
• a resin film with a release sheet which has the following property (I): [A] epoxy resin; [B] thermoplastic resin; [C] hardener; [D] particles containing large particles having a particle diameter exceeding 2A with respect to the average resin thickness A of the resin film; (I) peel resistance [X] (mN/20 mm) of the surface of the release sheet on which the resin is applied;
• the complex viscosity [Y] (MPa ⁇ s) of the resin composition at 25° C. is in a region satisfying the following formulas (1)-1 to (1)-4.
• the resin film with a release sheet according to any one of 1 to 5 above, which has the following property (II) and property (III): (II)
• the resin coverage of the resin film with release sheet immediately after coating is 95% or more;
• the magnification of the repelling on the resin film with release sheet shown in the following formula (2) is 6 times or less.
• the peeling rate of the resin composition from the release sheet is 95% or more.
• a resin film containing a resin having a predetermined amount of large particles having an average resin thickness of more than 2A and arranged on one side of a release sheet is obtained, which suppresses the spread of repellency, has good quality, and is easily peelable from the release sheet.
• the epoxy resin [A] used in the resin film with release sheet of the present invention is not particularly limited, and may be liquid or solid.
• examples include amine type epoxy resins, bisphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, resorcinol type epoxy resins, phenol aralkyl type epoxy resins, naphthol type epoxy resins, dicyclopentadiene type epoxy resins, epoxy resins with a biphenyl skeleton, isocyanate modified epoxy resins, tetraphenylethane type epoxy resins, triphenylmethane type epoxy resins, etc.
• amine-type epoxy resins and bisphenol-type epoxy resins which have an excellent balance between heat resistance and adhesiveness.
• these epoxy resins may be self-curing when heated, or may contain a hardener or hardening accelerator.
• amine-type epoxy resin trifunctional or tetrafunctional amine-type epoxy resins are preferably used, such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylylenediamine, and their halogen- and alkinol-substituted and hydrogenated products.
• epoxy resins may be used alone or in appropriate combination.
• the combination of glycidylamine type epoxy resin and bifunctional glycidyl ether type epoxy resin is particularly preferred because it has both heat resistance and moisture absorption resistance.
• Bisphenol type epoxy resins are bisphenol compounds in which the two phenolic hydroxyl groups have been glycidylated, and examples include bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and halogen- or alkyl-substituted or hydrogenated versions of these bisphenols.
• examples include bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and halogen- or alkyl-substituted or hydrogenated versions of these bisphenols.
• high molecular weight compounds having multiple repeating units can also be suitably used.
• thermoplastic resin [B] used in the resin film with release sheet of the present invention is not particularly limited, but if the epoxy resin [A] is liquid, it dissolves in the epoxy resin when preparing the resin composition, and forms the resin composition together with the epoxy resin.
• Specific compounds of the thermoplastic resin [B] that are preferably used include polyethersulfone, polysulfone, polyimide, polyetherimide, polycarbonate, polyetherethersulfone, polyvinyl formal, polymethyl methacrylate, etc.
• the curing agent [C] for the resin used in the resin film with release sheet of the present invention may be any compound having an active group capable of reacting with an epoxy group.
• the curing agent include aromatic amines, dicyandiamide, and dibasic acid dihydrazides, either alone or in mixtures. Of these, aromatic amines are preferred, and specific examples of such compounds include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and metaxylenediamine.
• Aromatic amines are particularly preferred because they can impart heat resistance to the cured resin.
• the [D] particles used in the resin film with release sheet of the present invention are large-sized particles having a particle size exceeding 2A relative to the average resin thickness A of the resin film, and the particles are at least partially insoluble in the epoxy resin composition.
• large-sized particles having a particle size exceeding 2A relative to the average resin thickness A of the resin film may be abbreviated as [D] particles.
• these particles include any type of particle, such as metal particles, rubber particles, thermoplastic resin particles, and inorganic particles, and generally, particles that are insoluble in the epoxy resin composition and can exist as particles in the cured resin are used.
• Examples of materials include acrylic, polyamide, polyimide, polyaramid, polyester, polycarbonate, polyphenylene sulfide, polybenzimidazole, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polyacetylene, polyaniline, polypyrrole, polythiophene, polyisothianaphthene, polyethylenedioxythiophene, carbon, silica, titania, alumina, zirconia, tungsten trioxide, vanadium pentoxide, barium titanate, potassium titanate, and various metal fine particles. These particles may also be a combination of any number of materials. For example, particles in which a core of an inorganic or organic material is coated with a metal material are exemplified.
• multiple types of particles can be used simultaneously, and a particulate filler that does not contain large particles can also be used in addition to the particles [D]. Note that the presence or absence of large particles is evaluated separately for each particle component.
• the particles are contained in an amount of 10 to 30% by mass relative to the entire resin composition.
• the amount of particles contained in the resin composition is preferably 25% by mass or less.
• the shape of the particles is preferably spherical in order to prevent deterioration of the quality of the resin film.
• 40 particles are examined under a microscope, and when 90% or more of the particles have a circularity of 1.1 or less, the particles are considered to be spherical.
• the circularity can be calculated by dividing the maximum radius of the particles by the minimum radius in accordance with JIS B 0621:1984.
• the particles according to the present invention include large-diameter particles, but whether or not they are large-diameter particles is determined by the relationship with the resin thickness arranged on one side of the release sheet in the resin film, and particles with a diameter exceeding 2A (unit: ⁇ m, etc.) with respect to the average resin thickness A (unit: ⁇ m, etc.) are called large-diameter particles.
• the content of large particles among the [D] particles can be 1% or more of the total amount of [D] particles in the particle size distribution shown on a number basis, and the functionality of the large particles can be expressed, but in order to express a sufficient effect, it is preferable that it is 10% or more, and the upper limit side is preferably 30% or less.
• the preferred upper limit of the content of large particles is more preferably 25% or less, and even more preferably 20% or less.
• the content of large particles (>2A) referred to here can be determined from data on 2000 or more particles that can be observed by magnifying the resin film 300 times and examining any position under a microscope. If the content of large particles in the particles according to the present invention is less than 10% of the total amount of [D] particles on a number basis, it may be difficult to obtain sufficient functionality from the particles when the resin film is laminated. Furthermore, if the content of large particles in the particles according to the present invention is more than 30% of the total amount of [D] particles on a number basis, the probability of particles coming into contact with each other in the resin film may increase, and the quality of the resin film may deteriorate.
• the particle size used in determining the particle size distribution i.e., the particle size of each particle counted in the present invention, is the average diameter of the maximum and minimum diameters of each particle that can be observed by microscope, and the particle size distribution is calculated using particles with an average diameter of 1 ⁇ m or more.
• the density of the particles [D] is preferably 1.0 g/ cm3 or more and 2.0 g/ cm3 or less.
• classification may be performed using a dry classification device (e.g., a TTSP separator (manufactured by Hosokawa Micron Corporation)) to obtain particles of a specified diameter.
• a dry classification device e.g., a TTSP separator (manufactured by Hosokawa Micron Corporation)
• the particles used in the present invention can be dispersed in the resin by ordinary mixing operations.
• the resin composition used in the resin film of the present invention can contain, in addition to the above components, one or more of the following liquid thermosetting resins other than epoxy resins, curing accelerators, flame retardants, and silane coupling agents, as necessary.
• characteristic (I) The relationship between the peel resistance [X] of the surface on which the resin is placed in the release sheet according to the present invention and the complex viscosity [Y] of the resin composition at 25°C exists in a region that satisfies the following formulas (1)-1 to (1)-4.
• the relationship between the peel resistance [X] of the surface on which the resin is disposed in the release sheet according to the present invention and the complex viscosity [Y] of the resin composition at 25°C exists in a region that satisfies the following formulas (1)-1, (1)-2', (1)-3, and (1)-4'.
• the peel resistance [X] of the surface of the release sheet on which the resin is placed is a value obtained by measuring as follows: A rectangular release sheet 250 mm wide and 90 mm long is fixed to a flat surface, and an adhesive consisting of an acrylic emulsion is applied to the surface. The thickness of the coating should be 125 ⁇ m in a wet state immediately after coating. Immediately after coating, the adhesive is baked and dried by heating at 100°C for 120 seconds. Next, a PET film is attached to the adhesive-coated surface of the dried release sheet. This attachment is performed, for example, by moving a 7.5 kg rubber roller back and forth once, utilizing the weight of the rubber roller. Next, the film is left at 23°C and 50% R.H.
• test piece 20 mm wide and 250 mm long is cut out, and the test piece is subjected to a 180° peel peel in accordance with the method specified in JIS Z 0237:2009 "Test methods for adhesive tapes and adhesive sheets", except that the peel speed is changed to 1000 mm/min.
• the simple average value of the force at this time is the peel resistance.
• the complex viscosity [Y] of the resin composition at 25°C refers to the complex viscosity at 25°C read from the viscoelasticity curve obtained by using a dynamic viscoelasticity measuring device (e.g., ARES-G2: manufactured by TA Instruments, etc.) with parallel plates, simply raising the temperature from 10°C at a heating rate of 2°C/min, and measuring at a frequency of 77.25 Hz and a plate interval of 0.5 mm.
• ARES-G2 manufactured by TA Instruments, etc.
• Each of the formulas (1) is obtained from a Y-axis semi-logarithmic graph in which the X-axis represents peel resistance [X] and the Y-axis represents complex viscosity [Y], with the Y-axis being a logarithmic scale.
• the coefficient in the exponent part of the exponential function e represents the slope of the Y-axis semi-logarithmic graph represented by the above formula.
• the coefficient in the exponent part of such an exponential function e may be expressed as follows, with E representing a power of 10. For example, "-7E-04" indicates -0.0007, and represents the slope of the Y-axis semi-logarithmic graph expressed by the above formula.
• the resin composition used in the present invention contains the [D] particles as an essential component, and it is preferable that 75% or less of the particles have a particle size distribution expressed on a number basis that is larger than the average resin thickness A of the resin arranged on one side of the release sheet.
• the release sheet is turned down, a difference in height occurs between the resin present above the particles and the resin present to the side of the particles that is not above the particles, etc., and the resin composition is more likely to be subjected to the expansion force. Therefore, repelling is more likely to occur and to expand over time.
• a low peel resistance [X] of the release sheet is preferable because it is easier to peel off from the resin film, but in the present invention, large particle diameter particles are used, so if the peel resistance [X] is too low, the force holding the resin composition on the release sheet is smaller and the expansion force of the resin composition increases, resulting in more repelling and a faster expansion of the repelling over time, which deteriorates the quality of the resin film.
• the present invention has found that in order to suppress the expansion force of the resin composition and suppress the generation and spread of repellency, it is preferable to increase the complex viscosity [Y] of the resin composition to a certain extent.
• the adsorption force of the [D] particles is preferably 0.3 mN/m to 17.8 mN/m, more preferably 0.5 mN/m to 10 mN/m, and even more preferably 1.0 mN/m to 5 mN/m.
• the above adsorption force is measured by applying an adhesive to the probe side of a Si cantilever of an AFM (e.g., a scanning probe microscope SPM manufactured by Bruker), attaching the particles and leaving them to stand for 1 hour to fix them, contacting them with a sapphire substrate washed with ethanol, and measuring the retention time of 0 seconds, the load speed of 300 nm/s, room temperature, and humidity of 20% to 40%.
• an adhesive e.g., a scanning probe microscope SPM manufactured by Bruker
• the peel resistance [X] of the release sheet is specifically set to 500 mN/20 mm or more, which suppresses the expansion force of the resin composition and the expansion of the resin repelling.
• the peel resistance [X] of the release sheet is set to 4000 mN/20 mm or less, which improves the releasability of the resin from the release sheet.
• the complex viscosity [Y] of the resin composition at 25°C is specifically set to 0.01 MPa ⁇ s or more, which suppresses the expansion force of the resin composition and the expansion of the repelling on the resin film, and is preferably 0.08 MPa ⁇ s or more.
• the complex viscosity [Y] by setting the complex viscosity [Y] to 2.1 MPa ⁇ s or less, the handling properties when placed on the release sheet can be maintained good. From this perspective, it is more preferable to set the complex viscosity [Y] to 1 MPa ⁇ s or less.
• the balance between the peel resistance [X] of the release sheet and the complex viscosity [Y] of the resin composition at 25 ° C. is important.
• the release sheet in a combination of peel resistance [X] of 500 mN/20 mm and complex viscosity [Y] of 0.01 MPa ⁇ s, the release sheet cannot completely suppress the expansion force of the resin composition, and the repelling increases, resulting in poor quality.
• the average resin thickness A of the resin film with release sheet of the present invention is preferably 50 ⁇ m or less.
• the above thickness is obtained by lowering the temperature below the glass transition point of the resin in a resin film state in which the resin is coated on the release sheet to make it into a glass state, and calculating the average value of the thickness of the resin film at 10 arbitrarily selected points using a micrometer (for example, Mitutoyo Coolantproof Micrometer, MDC-25MX), and calculating the difference between the average value of the thickness at 10 arbitrarily selected points of a separately measured release sheet (the resin may be removed from the resin film with release sheet and measured).
• a micrometer for example, Mitutoyo Coolantproof Micrometer, MDC-25MX
• the average resin thickness A By setting the average resin thickness A to 50 ⁇ m or less, it can be used to manufacture thin and lightweight parts even when the resin film is laminated and used.
• the lower limit of the average resin thickness A is not particularly limited, but it is preferably 5 ⁇ m or more. That is, the large particles contained in the [D] particles are preferably 10 ⁇ m or more. Also, the maximum particle size of the large particles is preferably 120 ⁇ m or less.
• the resin film with release sheet of the present invention preferably has characteristic (II) of 95% or more immediately after coating, and the magnification of the repellency on the resin film with release sheet, as shown in the following formula (2), is 6 times or less.
• the resin coverage rate of a resin film with a release sheet can be determined by inspecting the surface of the resin film from the resin film side at a magnification of 50 times, measuring the area of the resin composition covering the release sheet in an arbitrarily selected 10 mm x 10 mm square area of the resin film as the unit area, and calculating the ratio of this area to the unit area.
• the magnification rate of the repelling can be calculated by examining the surface of a resin film obtained by coating a release sheet with a resin composition at a magnification of 200 times and observing one randomly selected repelling area at a fixed point, taking the ratio of the area of the repelling area immediately after coating to the area of the repelling area 24 hours after coating, and can be expressed by the above formula (2).
• the area ratio is obtained by observing 10 randomly selected repelling areas, and the average value is taken as the magnification rate of the repelling.
• the magnification of the repellency is preferably 6 times or less. If it exceeds 6 times, when the resin film with release sheet is attached to the substrate, uncoated areas will be generated, resulting in defects and the required properties will not be obtained.
• the magnification is preferably 4 times or less, and more preferably 3 times or less.
• the parameter related to characteristic (II) can also be confirmed by using the same release sheet and resin composition as the target resin film with release sheet, applying the resin composition to the release sheet using a knife coater, and measuring and confirming the parameter by the above method immediately after coating and 24 hours after coating.
• the resin film with release sheet of the present invention has a characteristic (III) of a peeling rate of the resin composition from the release sheet of 95% or more.
• the peeling rate of the resin composition from the release sheet is measured as follows. The resin film is cut into strips 25 mm wide and 300 mm long to prepare test pieces. Next, an evaluation tape (e.g., Damlon Tape No. 3201R, manufactured by Nitto Denko Corporation) having the same shape as the cut test piece and an adhesive strength of 8.1 N/25 mm, and measuring 25 mm wide and 300 mm long, is attached to the side of the test piece on which the resin is placed, by moving a 2 kg rubber roller back and forth once.
• an evaluation tape e.g., Damlon Tape No. 3201R, manufactured by Nitto Denko Corporation
• a stainless steel support is attached to the side of the test piece on which the evaluation tape is attached, using double-sided tape.
• the support is attached to a tensile tester, and the evaluation tape is peeled off at an angle of 90° to the longitudinal direction of the test piece at a tensile speed of 10,000 mm/min in an atmosphere of 25°C and 50% RH.
• the entire test piece after peeling is photographed and the image is binarized to measure the area of the resin composition that does not cover the release sheet, and the peeling rate is calculated by dividing this by the area of the entire test piece.
• the resin film with release sheet according to the present invention preferably has a peeling rate of 95%, and particularly preferably 98% or more, as characteristic (III). If the peeling rate is less than 95%, uncoated areas that become defects may occur when the resin film with release sheet is attached to a substrate and the release sheet is peeled off.
• the present invention has both the above characteristics (II) and (III).
• Epoxy Resin Tetraglycidyldiaminodiphenylmethane, "Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.) Bisphenol F type liquid epoxy resin (EPICLON (registered trademark)) 830, manufactured by DIC Corporation.
• ⁇ Particulate filler (not including large particles)> Polyamide particles, "Orgasol (registered trademark) 1002D” (manufactured by Arkema Co., Ltd.) does not contain particles larger than 54 ⁇ m.
• silicone was used as the release agent, and the composition of the silicone, the amount applied, and the conditions of drying after coating on the release paper, heat treatment, etc. were adjusted to use release paper with the peel resistance shown in Table 1.
• ⁇ Peeling resistance> A rectangular release sheet with a width of 250 mm and a length of 90 mm is fixed on a flat surface, and an adhesive made of an acrylic emulsion is applied to the surface. The thickness of the coating is 125 ⁇ m in a wet state immediately after coating. After coating, the adhesive is baked and dried by heating at 100° C. for 120 seconds. Then, a PET film is attached to the adhesive-coated surface of the release sheet after drying. This attachment is performed by moving a 7.5 kg rubber roller back and forth once, utilizing the weight of the rubber roller. Then, after leaving it in an atmosphere of 23° C.
• test piece with a width of 20 mm and a length of 250 mm is cut out, and the test piece is peeled at 180° according to the method specified in JIS Z 0237:2009 "Test method for adhesive tape and adhesive sheet", except that the peel speed is changed to 1000 mm/min, and the simple average value of the force at that time is taken as the peel resistance.
• the complex viscosity at 25°C is determined from the viscoelasticity curve obtained by using a dynamic viscoelasticity measuring device (ARES-G2: manufactured by TA Instruments) with parallel plates, simply raising the temperature from 10°C at a heating rate of 2°C/min, measuring at a frequency of 77.25 Hz, a plate interval of 0.5 mm, and a strain of 0.17%.
• AWS-G2 dynamic viscoelasticity measuring device
• ⁇ Magnification of repellency on resin film with release sheet The surface of the resin film obtained by coating the resin composition on a release sheet is inspected at a magnification of 200 times, and one randomly selected repellent area is observed at a fixed point. The ratio of the area of the repellent area immediately after coating to the area of the repellent area 24 hours after coating is calculated and calculated according to the following formula (2). The area ratios are obtained for 10 randomly selected repellents, and the average value is calculated.
• ⁇ Removal rate of resin composition from release sheet> The resin film is cut into a strip of 25 mm wide and 300 mm long to prepare a test piece. Next, a 2 kg rubber roller is used to roll an evaluation tape of the same shape as the cut test piece, 25 mm wide and 300 mm long, with an adhesive strength of 8.1 N/25 mm, Damlon Tape No. 3201R (manufactured by Nitto Denko Corporation), on the side where the resin is arranged.
• the tape is attached to the surface of the test piece to which the evaluation tape is attached, using double-sided tape to attach a stainless steel support.
• the support is attached to a tensile tester, and the evaluation tape is peeled off in the longitudinal direction of the test piece at a tensile speed of 10,000 mm/min in an atmosphere of 25°C and 50% RH.
• the entire test piece after peeling is photographed, and the image is binarized to measure the area where the resin composition does not cover the release sheet, and the peeling rate is calculated by dividing the area by the entire area of the test piece.
• Examples 1-7 The compounds with the composition shown in Table 1 were used as raw materials and kneaded in a kneader to obtain a resin composition.
• the obtained resin composition was placed on one side of a release sheet to obtain a resin film with a release sheet.
• the peel resistance of the release sheet [X], the complex viscosity of the resin composition at 25°C [Y], the resin coverage of the resin film with a release sheet immediately after coating, the expansion rate of repelling, and the peel rate of the resin composition from the release sheet were as shown in Table 1.
• Comparative Example 1 A resin film with a release sheet was obtained in the same manner as in Example 2, except that the release sheet was the same as in Example 4 and the peel resistance [X] was set relatively low as shown in Table 1.
• the complex viscosity [Y] did not satisfy Y ⁇ 0.14e -7E-04X (1)-3.
• the resin coverage rate, the expansion rate of repellency, and the peel rate of the resin composition from the release sheet were evaluated under the same conditions as in Examples 1 to 7, and were as shown in Table 1.
• Example 2 A resin film with a release sheet was obtained in the same manner as in Example 3, except that the release sheet was the same as in Example 4 and the peel resistance [X] was set relatively low as shown in Table 1.
• the complex viscosity [Y] did not satisfy Y ⁇ 0.14e -7E-04X (1)-3.
• the resin coverage rate, the expansion rate of repellency, and the peel rate of the resin composition from the release sheet were evaluated under the same conditions as in Examples 1 to 7, and were as shown in Table 1.
• the present invention is suitable for use in parts that require thermal conductivity and are obtained by laminating resin films, but its scope of application is not limited to these.

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