WO2020059456A1 - Feuille de résine de silicone ignifuge, feuille de résine de silicone ignifuge dotée d'une couche adhésive, et feuille de résine de silicone ignifuge dotée d'une couche de substrat - Google Patents

Feuille de résine de silicone ignifuge, feuille de résine de silicone ignifuge dotée d'une couche adhésive, et feuille de résine de silicone ignifuge dotée d'une couche de substrat Download PDF

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Publication number
WO2020059456A1
WO2020059456A1 PCT/JP2019/033897 JP2019033897W WO2020059456A1 WO 2020059456 A1 WO2020059456 A1 WO 2020059456A1 JP 2019033897 W JP2019033897 W JP 2019033897W WO 2020059456 A1 WO2020059456 A1 WO 2020059456A1
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Prior art keywords
silicone resin
flame
resin sheet
retardant silicone
retardant
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PCT/JP2019/033897
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English (en)
Japanese (ja)
Inventor
裕介 杉野
崇 井元
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日東電工株式会社
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Priority claimed from JP2019153460A external-priority patent/JP7341792B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2020059456A1 publication Critical patent/WO2020059456A1/fr

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    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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 flame-retardant silicone resin sheet.
  • the present invention also relates to a flame-retardant silicone resin sheet having a pressure-sensitive adhesive layer having a flame-retardant silicone resin sheet and a pressure-sensitive adhesive layer.
  • the present invention also relates to a flame-retardant silicone resin sheet with a substrate layer having a flame-retardant silicone resin sheet and a substrate layer.
  • a halogen-based flame retardant has been widely used as a flame retardant for making a paint composition flame retardant (see Patent Document 1).
  • this method is not preferable in terms of environmental protection because of the problem of dioxin and chlorofluorocarbon generated from the halogenated flame retardant.
  • inorganic flame retardants such as aluminum hydroxide have been used as flame retardants for making the coating composition flame retardant.
  • aluminum hydroxide has a problem that physical properties such as physical properties and water resistance of the paint and the substrate coated with the paint are deteriorated.
  • inorganic paints have low flexibility and are easily broken, it is difficult to coat them with a thick film. Therefore, although the paint itself has flame retardancy, in the case of a composite with plastic, heat due to flame contact is transmitted to the plastic, and the plastic is carbonized or spread. In the case of a paint containing an organic binder, the organic binder is carbonized during flame contact. Therefore, it is difficult to use plastics coated with these paints in applications requiring non-carbonization, such as railway vehicles.
  • a glass fiber sheet in which an inorganic coating agent is applied is known.
  • a general inorganic coating agent applied to a glass fiber sheet, or impregnated, when the binder contains an organic component there is a problem of low nonflammability, when the binder is an inorganic component, There are drawbacks of low flexibility and fragility.
  • a light diffusion sheet including at least one glass fiber fabric and a pair of resin layers sandwiching the glass fiber fabric, wherein the resin layer is made of a thermosetting resin such as vinyl ester or a photocurable resin.
  • a sheet is disclosed (see Patent Document 2). Further, a glass comprising at least one glass fiber woven fabric, a resin coating layer made of a thermosetting resin formed by impregnating and solidifying the glass fiber woven fabric, and a bead layer on at least one surface of the resin coating layer.
  • a fiber sheet is disclosed (see Patent Document 3). However, all of these light diffusion sheets have insufficient nonflammability and low flexibility.
  • a flame-retardant composite member having a coating formed from a silicone resin composition containing at least one condensation-reactive silicone resin containing inorganic oxide particles on at least one surface of a plastic-based substrate containing an inorganic compound has been reported.
  • the coating film exhibits high flame retardancy by containing the above-mentioned specific inorganic oxide particle-containing condensation-reactive silicone resin.
  • the above coatings are brittle and have poor elongation.
  • the coating is easily damaged by an external impact such as when an object from the outside hits, or the above-mentioned coating or the flame-retardant composite member having the coating is attached to an adherend to be made flame-retardant in a sheet shape.
  • the coating surface is easily damaged during the attaching operation, and a problem that the above-described coating and the flame-retardant composite member having the coating are easily cracked when bent in a sheet shape.
  • the flame-retardant silicone resin sheet of the present invention A flame-retardant silicone resin sheet formed from a silicone resin composition containing a silicone resin and glass frit,
  • the pencil hardness specified in JIS K 5600-5-4: 1999 on the surface of the flame-retardant silicone resin sheet is a hardness of F or more.
  • the pencil hardness is H or higher.
  • the flame-retardant silicone resin sheet of the present invention has a breaking strength of 3.2 MPa or more at a temperature of 23 ° C., a humidity of 50% RH, a tensile speed of 200 mm / min, and a distance between chucks of 50 mm.
  • the flame-retardant silicone resin sheet of the present invention has a breaking elongation of 2.2% or more at a temperature of 23 ° C., a humidity of 50% RH, a tensile speed of 200 mm / min, and a distance between chucks of 50 mm.
  • the flame-retardant silicone resin sheet of the present invention has a total calorific value per 10 minutes of 30 MJ / m 2 or less in a cone calorimeter test according to ISO 5660-1: 2002, and a maximum heat generation rate. Is 300 kW / m 2 or less, and the ignition time is 60 seconds or more.
  • the silicone resin is an addition reaction type silicone.
  • the silicone resin is a silicone rubber.
  • the content of the glass frit in the silicone resin composition is 0.1 part by weight to 500 parts by weight based on 100 parts by weight of the silicone resin.
  • the flame-retardant silicone resin sheet of the present invention has a thickness of 5 ⁇ m to 5000 ⁇ m.
  • the flame-retardant silicone resin sheet with a pressure-sensitive adhesive layer of the present invention has the flame-retardant silicone resin sheet of the present invention and a pressure-sensitive adhesive layer.
  • the flame-retardant silicone resin sheet with the pressure-sensitive adhesive layer of the present invention has a thickness of 6 ⁇ m to 6000 ⁇ m.
  • the flame-retardant silicone resin sheet with a substrate layer of the present invention has the flame-retardant silicone resin sheet of the present invention and a substrate layer.
  • an adhesive layer is provided between the flame-retardant silicone resin sheet and the base layer.
  • the flame-retardant silicone resin sheet with a base material layer of the present invention has a thickness of 20 ⁇ m to 10000 ⁇ m.
  • an object of the present invention is to provide a flame-retardant silicone resin sheet which exhibits high flame retardancy, is hardly scratched on its surface, and hardly cracks when bent. Further, an object of the present invention is to provide a flame-retardant silicone resin sheet having an adhesive layer having such a flame-retardant silicone resin sheet and an adhesive layer. Furthermore, an object of the present invention is to provide a flame-retardant silicone resin sheet with a base layer having such a flame-retardant silicone resin sheet and a base layer.
  • FIG. 1 is a schematic sectional view showing an example of the flame-retardant silicone resin sheet with an adhesive layer of the present invention.
  • FIG. 2 is a schematic sectional view showing an example of the flame-retardant silicone resin sheet with a base material layer of the present invention.
  • FIG. 3 is a schematic sectional view showing another example of the flame-retardant silicone resin sheet with a base material layer of the present invention.
  • FIG. 4 is a perspective view of the combustion test device used in the combustion test.
  • FIG. 5 is a schematic diagram of a combustion test device used in the cone calorimeter test.
  • the flame-retardant silicone resin sheet of the present invention is formed from a silicone resin composition containing a silicone resin and a glass frit.
  • the flame-retardant silicone resin sheet of the present invention is a sheet formed from the above-mentioned silicone resin composition, and any suitable forming method can be adopted as a forming method within a range that does not impair the effects of the present invention.
  • a forming method for example, the above-mentioned silicone resin composition is applied on any appropriate base material (for example, a polyethylene terephthalate film) so that the thickness after drying becomes a desired thickness, and dried by heating. Thereafter, a method of forming a sheet-like flame-retardant silicone resin sheet by peeling the above-mentioned base material may be used.
  • the silicone resin composition may be a solvent-based composition, a water-dispersed composition, or a non-solvent-based composition (for example, a hot melt-based composition). Good.
  • silicone resin composition examples include kiss coating, gravure coating, bar coating, spray coating, knife coating, wire coating, dip coating, die coating, curtain coating, dispenser coating, screen printing, metal mask printing, and the like. And any suitable application method.
  • the flame-retardant silicone resin sheet of the present invention is typically formed by curing the above-mentioned silicone resin composition into a sheet.
  • the composition of the flame-retardant silicone resin sheet of the present invention is not typically the same as the composition of the flame-retardant silicone resin sheet of the present invention.
  • the flame-retardant silicone resin sheet of the present invention has a pencil hardness of not less than F, preferably not less than H, more preferably not less than 2H as defined by JIS K 5600-5-4: 1999 on the surface thereof. It is. If the pencil hardness of the surface of the flame-retardant silicone resin sheet of the present invention specified in JIS K 5600-5-4: 1999 falls within the above range, the surface is hardly scratched and hardly cracked even when bent. And a flame-retardant silicone resin sheet.
  • the hardness of the pencil used for measuring the pencil hardness is typically, for example, 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, and 6H (there may be a softer hardness than 6B or a harder hardness than 6H).
  • the surface of a flame-retardant silicone resin sheet is designed so that the pencil hardness specified in JIS K 5600-5-4: 1999 is equal to or higher than a specific hardness, so that the surface can be scratched.
  • a flame-retardant silicone resin sheet that is difficult to adhere and that is less likely to crack even when bent. That is, in preparing a silicone resin composition containing a silicone resin and a glass frit, the pencil hardness specified by JIS K 5600-5-4: 1999 on the surface of a flame-retardant silicone resin sheet formed therefrom is a specific hardness.
  • a silicone resin as described above is selected and prepared, it is possible to provide a flame-retardant silicone resin sheet that does not easily crack even when bent. Since the measurement of the pencil hardness specified in JIS K 5600-5-4: 1999 can be performed extremely easily, JIS K 5600-5-4: 1999 on the surface of various obtained flame-retardant silicone resin sheets can be obtained. No significant effort is required to measure the pencil hardness as specified in. Further, as described later, since there is a preferred silicone resin for further exhibiting the effects of the present invention, there is no need to select from a myriad of silicone resins.
  • the flame-retardant silicone resin sheet of the present invention has a breaking strength at a temperature of 23 ° C., a humidity of 50% RH, a tensile speed of 200 mm / min and a distance between chucks of 50 mm, preferably 3.2 MPa or more, more preferably 3.5 MPa. Or more, more preferably 4.0 MPa or more, and particularly preferably 4.5 MPa or more.
  • the upper limit of the breaking strength is preferably 50 MPa or less.
  • the flame-retardant silicone resin sheet of the present invention has a breaking elongation at a temperature of 23 ° C., a humidity of 50% RH, a tensile speed of 200 mm / min and a distance between chucks of 50 mm, preferably 2.2% or more, more preferably 2% or more. 0.5% or more, more preferably 3.0% or more, further preferably 4.0% or more, particularly preferably 5.0% or more, and most preferably 6.0% or more. .
  • the upper limit of the breaking elongation is preferably 1000% or less. When the elongation at break is in the above range, it is possible to provide a flame-retardant silicone resin sheet that is less likely to be scratched on the surface and is less likely to crack when bent.
  • the flame-retardant silicone resin sheet of the present invention preferably has a total calorific value per 10 minutes of 30 MJ / m 2 or less and a maximum heat generation rate of 300 kW / m in a cone calorimeter test according to ISO 5660-1: 2002. 2 or less, the ignition time is 60 seconds or more.
  • the result of the cone calorimeter test of the flame-retardant silicone resin sheet of the present invention falls within the above range, a flame-retardant silicone resin sheet exhibiting higher flame retardancy can be provided.
  • the thickness of the flame-retardant silicone resin sheet of the present invention is preferably from 5 ⁇ m to 5000 ⁇ m, more preferably from 10 ⁇ m to 4000 ⁇ m, still more preferably from 20 ⁇ m to 3000 ⁇ m, and particularly preferably from 30 ⁇ m to 2000 ⁇ m.
  • the thickness of the flame-retardant silicone resin sheet of the present invention is within the above range, the effects of the present invention can be further exhibited.
  • the flame-retardant silicone resin sheet of the present invention may have a protective layer on the surface as long as the effects of the present invention are not impaired.
  • the main component of the protective layer is preferably a polymer.
  • the protective layer is preferably, for example, at least one selected from the group consisting of an ultraviolet-curable hard coat layer, a thermosetting hard coat layer, and an organic-inorganic hybrid hard coat layer.
  • Such a protective layer may be composed of only one layer, or may be composed of two or more layers.
  • the UV-curable hard coat layer can be formed from a resin composition containing a UV-curable resin.
  • the thermosetting hard coat layer can be formed from a resin composition containing a thermosetting resin.
  • the organic-inorganic hybrid hard coat layer can be formed from a resin composition containing an organic-inorganic hybrid resin.
  • the curable compound used in the resin as described above includes a silanol group, a precursor of a silanol group (for example, an alkoxysilyl group or a chlorosilyl group), an acryloyl group, a methacryloyl group, a cyclic ether group, and an amino group.
  • the resin composition capable of forming the hard coat layer may further contain any appropriate additive depending on the purpose.
  • additives include a photopolymerization initiator, a silane coupling agent, a release agent, a curing agent, a curing accelerator, a diluent, an antioxidant, a denaturing agent, a surfactant, a dye, a pigment, and discoloration.
  • examples include an inhibitor, an ultraviolet absorber, a softener, a stabilizer, a plasticizer, and an antifoaming agent.
  • the type, number and amount of additives contained in the resin composition capable of forming the hard coat layer can be appropriately set according to the purpose.
  • the thickness of the protective layer may be any appropriate thickness as long as the effects of the present invention are not impaired. Such a thickness is preferably 0.1 ⁇ m to 200 ⁇ m, more preferably 0.2 ⁇ m to 100 ⁇ m, and further preferably 0.5 ⁇ m to 50 ⁇ m.
  • the silicone resin composition contains a silicone resin and a glass frit.
  • the silicone resin may be only one kind or two or more kinds.
  • the glass frit may be only one kind or two or more kinds.
  • the silicone resin is such that the pencil hardness specified in JIS K 5600-5-4: 1999 on the surface of the flame-retardant silicone resin sheet formed from the silicone resin composition is not less than a specific hardness. What is necessary is just to select a silicone resin.
  • a silicone resin is preferably an addition-reaction-type silicone or a silicone rubber from the viewpoint that the effects of the present invention can be further exhibited.
  • silicone resins there are an addition reaction type silicone and a condensation reaction type silicone.
  • a silicone resin is selected such that the pencil hardness of the surface of the flame-retardant silicone resin sheet formed from the silicone resin composition specified in JIS K 5600-5-4: 1999 becomes a specific hardness or more.
  • such a silicone resin may be an addition reaction type silicone or a condensation reaction type silicone.
  • the silicone resin is preferably an addition-reaction-type silicone in that the effects of the present invention can be further exhibited.
  • silicone resin As a typical classification system of silicone resin, there are silicone rubber and silicone resin.
  • silicone resin a silicone resin is selected such that the pencil hardness of the surface of the flame-retardant silicone resin sheet formed from the silicone resin composition specified in JIS K 5600-5-4: 1999 becomes a specific hardness or more.
  • the silicone resin it may be a silicone rubber or a silicone resin.
  • the silicone resin is preferably silicone rubber.
  • Silicone resin is particularly preferably an addition-reaction-type silicone and silicone rubber in that the effect of the present invention can be further exhibited.
  • addition reaction type silicone examples include a one-component addition reaction type silicone and a two-component addition reaction type silicone, and preferably a two-component addition reaction type silicone.
  • addition reaction type silicone examples include, for example, a liquid two-liquid addition reaction type silicone rubber for LIMS manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-1950 series (for example, KE-1950-10A / B, KE-1950-20A / B, KE-1950-30A / B, KE-1950-35A / B, KE-1950-40A / B, KE-1950-50A / B, KE-1950-60A / B, KE- 1950-70A / B), KE-1987A / B, KE-1988A / B, KEG-2000 series, KEG-2001 series, KEG-2002 series, KEG-2003H series, KE-2017 series, KE-2019 series, KE-2090 series, KE-2096 series, KET-1001 series, etc.), Two-part addition reaction type RTV silicone rubber manufactured by Etsu Chemical Co., Ltd.
  • KE-1950 series for example, KE-1950-10A / B, KE-1950
  • KE-1204A / B KE-1280-A / B, KE-1282-A / B, KE-1283-A / B, KE -1285-A / B, KE-1897-A / B, KE-109EA / A / B, KE-106, KE-1011-A / B, KE-1012-A / B, KE-1013-A / B , KE-1051J-A / B, KE-1063-A / B, KE-1861-A / B, ASP-2010-A / B, KER-6110-A / B, ASP-1050P-A / B, ASP -1120-A / B, SCR-1012A / BR, SCR-1016A / B, SCR-1018A (S2) / B, FER-7061-A / B, FER-7110-A / B, KER-2500- A / B, KER 2500N-A
  • silicone adhesive (addition reaction type) (for example, KR-3700, KR-3701, X-40-3237-1, X-40-3240, X-40-3291-1, KR-3704) (X-40-3229), X-40-3323, X-40-3270-1, X-40-3306, etc.), LR7665 series manufactured by Asahi Kasei Wacker Silicone Co., Ltd., LR3033 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Series, TSE3032 series manufactured by Momentive, LSR series manufactured by Momentive, and the like.
  • silicone rubber specifically, for example, a liquid two-liquid addition reaction type silicone rubber for LIMS manufactured by Shin-Etsu Chemical Co., Ltd.
  • KE-1950 series for example, KE-1950-10A / B, KE- 1950-20A / B, KE-1950-30A / B, KE-1950-35A / B, KE-1950-40A / B, KE-1950-50A / B, KE-1950-60A / B, KE-1950- 70A / B
  • KE-1987A / B, KE-1988A / B KEG-2000 series, KEG-2001 series, KEG-2002 series, KEG-2003H series, KE-2017 series, KE-2019 series, KE- 2090 series, KE-2096 series, KET-1001 series, etc.
  • Shin-Etsu One-component addition reaction type RTV silicone rubber manufactured by Kogyo Co., Ltd.
  • KE-1831, KE-1833, KE-1835-S, KE-1850, KE-1854, KE-1855, KE-1880, KE-1884 KE-1885, IO-SEAL-300, KE-1014, KE-1056, KE-1057, KE-1061, KE-1062, KE-1842, KE-1844, KE-1886, KE-1871, KE-1867.
  • KE-1204A / B KE-1280-A / B, KE-1282-A / B, KE-1283-A / B, KE-1285-A / B, KE-1897-A / B, KE-109EA-A / B, KE-106, KE-1011-A / B, KE-1012-A / B, KE-1013-A / B, KE-1051JA / B, KE-1063-A / B, KE-1861-A / B, ASP-2010-A / B, KER-6110-A / B, ASP-1050P-A / B, ASP-1120-A / B, SCR-1012A / BR, SCR-1016A / B, SCR-1018A (S2) / B, FER-7061-A / B, FER-7110-A / B, KER-2500 -A / B, KE R-2500NA / B, KER
  • TV silicone rubbers for example, KE-4835, X-31-1273-2, X-31-1598-2, KER-4500, KER-4600, KER-4130M-UV, KER-4130H-UV, KER-4000- UV, SMP-7004, etc.).
  • the content of the silicone resin in the silicone resin composition is preferably from 15% by weight to 99% by weight, more preferably from 15% by weight to 99% by weight, based on the point that the effects of the present invention can be further exhibited. Is from 16 to 98% by weight, more preferably from 17 to 97% by weight, particularly preferably from 18 to 96% by weight.
  • the silicone resin composition contains a glass frit.
  • the deformation point of the glass frit is preferably from 300 ° C to 700 ° C, more preferably from 300 ° C to 650 ° C, even more preferably from 300 ° C to 600 ° C.
  • any appropriate glass frit can be adopted.
  • a glass frit is preferably an inorganic particle (glass frit) having sinterability, and more preferably silicic acid (or silicon oxide), boric acid (or boron oxide), borosilicate, Inorganic particles (glass frit) formed from at least one component selected from aluminum oxide, calcium oxide, sodium oxide, lithium oxide and phosphorus oxide.
  • Representative glass frits include phosphate glass frit, borosilicate glass frit, non-alkali glass frit, enamel frit, and the like.
  • Particularly preferred glass frit is a glass frit formed from a component containing at least phosphorus oxide.
  • the content of phosphorus oxide is preferably 5% by weight to 70% by weight, and the lower limit is preferably 10% by weight, more preferably 20% by weight. And the upper limit is preferably 60% by weight, more preferably 50% by weight.
  • the average particle size of the glass frit is preferably 0.1 ⁇ m to 1000 ⁇ m.
  • the lower limit of the average particle size of the glass frit is preferably 0.5 ⁇ m, more preferably 1 ⁇ m, and still more preferably 2 ⁇ m.
  • the upper limit of the average particle size of the glass frit is preferably 500 ⁇ m, more preferably 300 ⁇ m, and further preferably 150 ⁇ m.
  • the content of the glass frit in the silicone resin composition is preferably 0.1 to 500 parts by weight, more preferably 1 to 450 parts by weight, based on 100 parts by weight of the silicone resin. It is preferably from 5 to 400 parts by weight, particularly preferably from 10 to 350 parts by weight.
  • a flame-retardant silicone resin sheet exhibiting higher flame retardancy can be provided.
  • the silicone resin composition may contain, in addition to the silicone resin and the glass frit, any appropriate other components as long as the effects of the present invention are not impaired.
  • examples of such other components include a curing catalyst and a solvent.
  • the upper limit is preferably 95% by weight, more preferably 90% by weight, and the lower limit is preferably from the viewpoints of handleability, coatability, impregnation and the like. It is 30% by weight, more preferably 40% by weight.
  • the flame-retardant silicone resin sheet with a pressure-sensitive adhesive layer of the present invention has the flame-retardant silicone resin sheet of the present invention and a pressure-sensitive adhesive layer.
  • FIG. 1 is a schematic sectional view showing an example of the flame-retardant silicone resin sheet with an adhesive layer of the present invention.
  • a flame-retardant silicone resin sheet 1000 with an adhesive layer has a flame-retardant silicone resin sheet 100 and an adhesive layer 200.
  • the flame-retardant silicone resin sheet 100 and the pressure-sensitive adhesive layer 200 are directly laminated, but may have any other appropriate layer as long as the effects of the present invention are not impaired. May be.
  • the thickness of the flame-retardant silicone resin sheet with a pressure-sensitive adhesive layer of the present invention is preferably 6 ⁇ m to 6000 ⁇ m, more preferably 11 ⁇ m to 5000 ⁇ m, still more preferably 21 ⁇ m to 4000 ⁇ m, and particularly preferably 31 ⁇ m to 3000 ⁇ m. is there.
  • the pressure-sensitive adhesive layer a layer composed of any appropriate pressure-sensitive adhesive can be adopted.
  • adhesives include, for example, rubber-based adhesives (synthetic rubber-based adhesives, natural rubber-based adhesives, etc.), urethane-based adhesives, acrylic urethane-based adhesives, acrylic-based adhesives, silicone-based adhesives, Examples include a polyester-based adhesive, a polyamide-based adhesive, an epoxy-based adhesive, a vinylalkyl ether-based adhesive, and a fluorine-based adhesive.
  • the pressure-sensitive adhesive layer is preferably a silicone-based pressure-sensitive adhesive from the viewpoint that the curing of the present invention can be further developed. Such an adhesive may be only one kind, or two or more kinds.
  • Adhesives can be classified by adhesive form, for example, emulsion-type adhesives, solvent-type adhesives, ultraviolet-crosslinkable (UV-crosslinkable) adhesives, electron beam-crosslinkable (EB-crosslinkable) adhesives, and hot-melt adhesives. Agents (hot-melt pressure-sensitive adhesives) and the like. Such an adhesive may be only one kind, or two or more kinds.
  • the flame-retardant silicone resin sheet with a pressure-sensitive adhesive layer of the present invention can be produced by any appropriate method as long as the effects of the present invention are not impaired.
  • a production method includes, for example, (i) a flame-retardant silicone resin sheet formed on any appropriate substrate (for example, polyethylene terephthalate film) and another arbitrary substrate (for example, polyethylene).
  • a pressure-sensitive adhesive layer by applying the above materials (drying as necessary); (iii) a silicone resin on a pressure-sensitive adhesive layer formed on any appropriate substrate (eg, polyethylene terephthalate film)
  • a method of applying and curing the composition to produce a flame-retardant silicone resin sheet with an adhesive layer e.g, polyethylene terephthalate film
  • the flame-retardant silicone resin sheet with a substrate layer of the present invention has the flame-retardant silicone resin sheet of the present invention and a substrate layer.
  • FIG. 2 is a schematic sectional view showing an example of the flame-retardant silicone resin sheet with a base material layer of the present invention.
  • a flame-retardant silicone resin sheet 2000 with a base material layer has a flame-retardant silicone resin sheet 100 and a base material layer 300.
  • the flame-retardant silicone resin sheet 100 and the base material layer 300 are in a state of being directly laminated, but may have any other appropriate layer as long as the effects of the present invention are not impaired. May be.
  • the flame-retardant silicone resin sheet 2000 with the base material layer may be an embodiment having the pressure-sensitive adhesive layer 200 between the flame-retardant silicone resin sheet 100 and the base material layer 300.
  • the thickness of the flame-retardant silicone resin sheet with a substrate layer of the present invention is preferably from 20 ⁇ m to 10,000 ⁇ m, more preferably from 25 ⁇ m to 9000 ⁇ m, still more preferably from 35 ⁇ m to 8000 ⁇ m, particularly preferably from 45 ⁇ m to 7000 ⁇ m. is there.
  • the base material layer is preferably made of a plastic base material.
  • the plastic base material include a plastic sheet (which means not only a flat sheet but also a sheet having a three-dimensional curved surface) and a plate-like material (a plate having not only a flat plate-like material but also a three-dimensional curved surface).
  • Plastic substrate including a laminate including at least the plastic substrate.
  • plastic base material that is, a plastic material
  • thermoplastic resin and a thermosetting resin include a thermosetting resin.
  • thermoplastic resin examples include, for example, an olefin resin having an ⁇ -olefin as a monomer, such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA); polycarbonate ( PC); polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); polyvinyl chloride (PVC); vinyl acetate resins; styrene such as polystyrene, ABS resins, and AS resins Acrylic resin; Polyacrylonitrile; Polyphenylene sulfide (PPS); Amide resin such as polyamide (nylon) and wholly aromatic polyamide (aramid); Polyimide (PI); Polyamide imide (PAI); Tone (PEEK); Polyarylate (PAR); Polysulfone (PSF); Polyethersulfone (PES); Fluororesin
  • the material of the plastic base material that is, the plastic material
  • an olefin resin and a polycarbonate resin are preferable, and a polycarbonate resin is more preferable, from the viewpoint of particularly excellent flame retardancy.
  • a polycarbonate resin is more preferable, from the viewpoint of particularly excellent flame retardancy.
  • the plastic base material may contain an inorganic compound.
  • an inorganic compound include an inorganic flame retardant and an inorganic filler.
  • the inorganic flame retardant include metal hydroxides such as aluminum hydroxide and magnesium hydroxide; boron compounds; phosphorus compounds; antimony compounds; and sulfur flame retardants.
  • an inorganic compound is preferably an inorganic filler, and more preferably a glass fiber.
  • Such an inorganic compound may be used alone or in combination of two or more.
  • the content ratio of the inorganic compound in the plastic base material is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 45% by weight, and further preferably 3% by weight to 40% by weight. And particularly preferably from 5% by weight to 35% by weight. When the content ratio of the inorganic compound in the plastic base material is within the above range, the effects of the present invention can be further exhibited.
  • the content ratio of the plastic material in the plastic base material is preferably 50% by weight to 99.9% by weight, more preferably 55% by weight to 99% by weight, and further preferably 60% by weight to 97% by weight. And particularly preferably 65 to 95% by weight. When the content ratio of the plastic material in the plastic base material is within the above range, the effects of the present invention can be further exhibited.
  • the content ratio of the polycarbonate resin in the plastic material is preferably from 50% by weight to 100% by weight, more preferably from 70% by weight to 100% by weight, further preferably from 90% by weight to 100% by weight. Preferably it is from 95% to 100% by weight, most preferably substantially 100% by weight. When the content ratio of the polycarbonate resin in the plastic material is within the above range, the effects of the present invention can be further exhibited.
  • the base material may be subjected to any appropriate other flame retarding treatment.
  • a flame retarding treatment for example, addition of an organic flame retardant may be mentioned.
  • organic flame retardants include, for example, fluorine compounds, chlorine compounds, bromine compounds, phosphorus compounds, silicone compounds, sulfur flame retardants, and the like.
  • Such organic flame retardants may be used alone or in combination of two or more.
  • the flame-retardant silicone resin sheet with a substrate layer of the present invention can be produced by any appropriate method as long as the effects of the present invention are not impaired.
  • a production method for example, in the case of the embodiment in which the flame-retardant silicone resin sheet and the substrate layer are directly laminated, (i) applying the silicone resin composition onto the substrate layer A method of curing to produce a flame-retardant silicone resin sheet with a substrate layer, (ii) applying the silicone resin composition onto any suitable substrate (eg, polyethylene terephthalate film) and curing it before curing.
  • a method of forming an adhesive layer between the flame-retardant silicone resin sheet and the base material layer In the case of an embodiment having the method, (iii) a method of attaching a substrate layer to the adhesive layer side of the flame-retardant silicone resin sheet with an adhesive layer, and (iv) applying a material for the adhesive layer on the substrate layer.
  • the flame-retardant silicone resin sheet, the flame-retardant silicone resin sheet with the pressure-sensitive adhesive layer, and the flame-retardant silicone resin sheet with the base layer of the present invention exhibit high flame retardancy, are hardly scratched on the surface, and are bent. It is difficult to crack even if it is used. Therefore, interior parts of transportation equipment such as railway vehicles, aircraft, automobiles, ships, elevators, escalators, etc. (interior parts for transportation equipment), building materials, display materials, home appliances, electronic circuit materials Available as Further, it can be suitably used as a lighting cover, especially a lighting cover as an interior member for a transport machine.
  • a silicone-based pressure-sensitive adhesive (trade name: KR-3700, solid content: 60% by weight, manufactured by Shin-Etsu Chemical Co., Ltd.) was subjected to a release treatment, and a polyethylene terephthalate film (thickness: 50 ⁇ m, trade name: MRS # 50) (Mitsubishi Plastics Co., Ltd.), using a tester Sangyo Co., Ltd. applicator so that the thickness after drying is 20 ⁇ m, and then heated and dried at 140 ° C for 2 minutes in a hot air circulation oven, An adhesive sheet was obtained.
  • Example 1 The silicone resin composition A obtained in Synthesis Example 1 was dried on a polyethylene terephthalate film (thickness: 50 ⁇ m, trade name: Lumirror S10, manufactured by Toray Industries Inc.) using an applicator manufactured by Tester Sangyo Co., Ltd. And then dried by heating in a hot air circulation oven at 80 ° C. for 2 minutes and 140 ° C. for 2 minutes to form a flame-retardant silicone resin sheet (1A) on a polyethylene terephthalate film. Formed. Thereafter, the polyethylene terephthalate film was peeled off to obtain a flame-retardant silicone resin sheet (1A).
  • Example 2 The surface of the flame-retardant silicone-based resin sheet (1A) formed on the polyethylene terephthalate film coated with the silicone resin composition A in Example 1 and the silicone-based pressure-sensitive adhesive sheet formed on the polyethylene terephthalate film in Synthesis Example 4
  • the flame-retardant silicone resin sheet with a pressure-sensitive adhesive layer (1B) was obtained by laminating the polyethylene terephthalate film with the surface coated with the pressure-sensitive adhesive.
  • Example 3 The surface of the pressure-sensitive adhesive layer of the flame-retardant silicone resin sheet (1B) with a pressure-sensitive adhesive layer obtained in Example 2 was attached to the glass fiber reinforced polycarbonate plate obtained in Synthesis Example 5 to form a base material layer. A flame-retardant silicone resin sheet (1C) was obtained.
  • Example 4 The silicone resin composition B obtained in Synthesis Example 2 was dried on a peeled polyethylene terephthalate film (thickness: 50 ⁇ m, trade name: MRS, manufactured by Mitsubishi Plastics, Inc.) using an applicator manufactured by Tester Sangyo Co., Ltd. After that, the film was coated so as to have a thickness of 250 ⁇ m, and then heated and dried in a hot air circulation oven at 80 ° C. for 10 minutes and at 140 ° C. for 10 minutes. 2A) was formed. Thereafter, the polyethylene terephthalate film was peeled off to obtain a flame-retardant silicone resin sheet (2A).
  • Example 5 The surface of the flame-retardant silicone resin sheet (2A) formed on the polyethylene terephthalate film coated with the silicone resin composition B in Example 4 and the silicone-based pressure-sensitive adhesive sheet formed on the polyethylene terephthalate film in Synthesis Example 4
  • the flame-retardant silicone resin sheet (2B) with the pressure-sensitive adhesive layer was obtained by laminating the surface coated with the pressure-sensitive adhesive and then peeling off the polyethylene terephthalate film.
  • Example 6 The surface of the pressure-sensitive adhesive layer of the flame-retardant silicone resin sheet (2B) with a pressure-sensitive adhesive layer obtained in Example 5 was attached to the glass fiber reinforced polycarbonate plate obtained in Synthesis Example 5, and a base material layer was provided. A flame-retardant silicone resin sheet (2C) was obtained.
  • the obtained silicone resin composition d is put into a 225 ml glass bottle, 150 g of zirconia beads having a particle size of 2 mm is added, and the mixture is taken with a paint shaker (product name “Scandex”, manufactured by LAU (Germany)) for 3 hours.
  • a silicone resin composition D was obtained.
  • the obtained silicone resin composition D was applied on one side of an A4 size polyethylene terephthalate film (Lumirror S10, manufactured by Toray Industries, Inc.) having a thickness of 75 ⁇ m so as to have a thickness of 30 ⁇ m, and cured at 120 ° C. for 1 hour. Was done.
  • a silicone resin composition D was applied to the opposite surface of the polyethylene terephthalate film so as to have a thickness of 30 ⁇ m, thereby producing a flame-retardant silicone resin sheet (C1D) with a base layer.
  • the flame-retardant silicone resin sheet, the flame-retardant silicone resin sheet with the pressure-sensitive adhesive layer, and the flame-retardant silicone resin sheet with the base layer prepared above were held at a 45 ° inclination as shown in FIG.
  • the fuel container (alcohol container) 12 is placed on a cork base (container receiving base) 13 so that the center of the bottom of the fuel container (alcohol container) 12 is located 25.4 mm vertically below the center of the lower surface of the specimen. Then, 0.5 cc of ethyl alcohol was added to No. 12, and the mixture was ignited and left for about 2 minutes until the fuel was burned out.
  • Example 1 (Corn calorimeter test) With respect to Examples 1, 3, 4, 6 and Comparative Examples 1 and 3, a square test piece having a side of 100 mm was cut out, and as shown in FIG. 5, a corn calorimeter was obtained by a method according to ISO 5660-1: 2002. The test piece was burned by irradiating a heat ray of 50 kW / m 2 for 10 minutes using the method.
  • 14 is an exhaust hood
  • 15 is a cone type heater
  • 16 is a test material
  • 17 is a test material holder.
  • the determination of combustion was made based on the total calorific value (MJ / m 2 ), maximum heat generation rate (kW / m 2 ), and ignition time (second) measured during the test time.
  • the ignition time was defined as the time from the start of the test until the first ignition was confirmed, assuming that the flame was present for 10 seconds or more after the flame was confirmed from the test piece. Criteria (1) Total heat generation for 10 minutes ⁇ : Total heat generation is 30 MJ / m 2 or less ⁇ : Total heat generation is 30 MJ / m 2 or more (2) Maximum heat generation rate for 10 minutes ⁇ : Maximum heat generation rate 300 kW / m 2 or less ⁇ : Maximum heat generation rate is 300 kW / m 2 or more (3) Ignition time ⁇ : Ignition time is 60 seconds or more ⁇ : Ignition time is less than 60 seconds
  • Pencil hardness generally refers to the hardness of the hardest pencil that did not produce scars, and in Examples 1 to 6, it means that scarring does not occur when a pencil of at least F is used.
  • the obtained film is soft
  • JP-A-2016-27069 In the pencil hardness test described in Japanese Patent Application Laid-Open Publication No. H06-157, there is no example in which the evaluation of five points of “no peeling on the surface” was made using the pencil of B. That is, the pencil of B always has a scar of a scratch.
  • the film obtained from the flame-retardant material described in JP-A-2016-27069 always produces a scar when a scratch test is performed using a pencil of F which is harder than B, and the film is expressed in the present invention.
  • a possible pencil hardness (the pencil hardness specified in JIS K 5600-5-4: 1999 on the surface is a hardness of F or more) has not been developed.
  • the flame-retardant silicone resin sheet, the flame-retardant silicone resin sheet with the pressure-sensitive adhesive layer, and the flame-retardant silicone resin sheet with the base layer of the present invention exhibit high flame retardancy, are hardly scratched on the surface, and are bent. It is difficult to crack even if it is used. Therefore, interior parts of transportation equipment such as railway vehicles, aircraft, automobiles, ships, elevators, escalators, etc. (interior parts for transportation equipment), building materials, display parts, home appliances, electronic circuit parts Available as Further, it can be suitably used as a lighting cover, especially a lighting cover as an interior member for a transport machine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de résine de silicone ignifuge (100) qui présente une grande ininflammabilité, est peu susceptible de présenter des rayures de surface, et est peu susceptible de craquer même lorsqu'elle est pliée. L'invention concerne également une feuille de résine de silicone ignifuge dotée d'une couche adhésive (1000), qui a ce type de feuille de résine de silicone ignifuge (100) et une couche adhésive (200). L'invention concerne en outre une feuille de résine de silicone ignifuge dotée d'une couche de substrat (2000), qui a ce type de feuille de résine de silicone ignifuge (100) et une couche de substrat (300). Cette feuille de résine de silicone ignifuge (100) est formée à partir d'une composition de résine de silicone contenant une résine de silicone et une fritte de verre. La dureté au crayon, telle que spécifiée dans JIS K5600-5-4 : 1999, d'une surface de la feuille de résine de silicone ignifuge est F ou plus dure.
PCT/JP2019/033897 2018-09-20 2019-08-29 Feuille de résine de silicone ignifuge, feuille de résine de silicone ignifuge dotée d'une couche adhésive, et feuille de résine de silicone ignifuge dotée d'une couche de substrat WO2020059456A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018-176027 2018-09-20
JP2018176027 2018-09-20
JP2019-153460 2019-08-26
JP2019153460A JP7341792B2 (ja) 2018-09-20 2019-08-26 難燃性シリコーン樹脂シート、粘着剤層付難燃性シリコーン樹脂シート、および、基材層付難燃性シリコーン樹脂シート

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209576A (ja) * 2012-03-30 2013-10-10 Nippon Steel & Sumikin Chemical Co Ltd シリコーン樹脂組成物、シリコーン樹脂硬化物、及び表示装置
WO2014038285A1 (fr) * 2012-09-05 2014-03-13 日本電気硝子株式会社 Corps stratifié de résine
JP2014231598A (ja) * 2013-05-01 2014-12-11 日東電工株式会社 難燃シートおよび難燃複合部材
JP2016027069A (ja) * 2014-06-26 2016-02-18 日東電工株式会社 難燃材料およびその用途

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209576A (ja) * 2012-03-30 2013-10-10 Nippon Steel & Sumikin Chemical Co Ltd シリコーン樹脂組成物、シリコーン樹脂硬化物、及び表示装置
WO2014038285A1 (fr) * 2012-09-05 2014-03-13 日本電気硝子株式会社 Corps stratifié de résine
JP2014231598A (ja) * 2013-05-01 2014-12-11 日東電工株式会社 難燃シートおよび難燃複合部材
JP2016027069A (ja) * 2014-06-26 2016-02-18 日東電工株式会社 難燃材料およびその用途

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