WO2009116302A1 - Composition de résine de polyester ignifuge et laminé ignifuge - Google Patents

Composition de résine de polyester ignifuge et laminé ignifuge Download PDF

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Publication number
WO2009116302A1
WO2009116302A1 PCT/JP2009/001253 JP2009001253W WO2009116302A1 WO 2009116302 A1 WO2009116302 A1 WO 2009116302A1 JP 2009001253 W JP2009001253 W JP 2009001253W WO 2009116302 A1 WO2009116302 A1 WO 2009116302A1
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Prior art keywords
layer
polyester resin
melamine
laminate
flame retardant
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PCT/JP2009/001253
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English (en)
Japanese (ja)
Inventor
田中一也
北山和彦
齋藤大嗣
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三菱樹脂株式会社
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Priority claimed from JP2008250453A external-priority patent/JP5368045B2/ja
Priority claimed from JP2008312184A external-priority patent/JP4856160B2/ja
Priority claimed from JP2008312185A external-priority patent/JP4648450B2/ja
Priority claimed from JP2009034116A external-priority patent/JP2009255543A/ja
Priority claimed from JP2009051922A external-priority patent/JP2010205648A/ja
Priority claimed from JP2009055760A external-priority patent/JP2010208112A/ja
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to CN2009801103214A priority Critical patent/CN101977989A/zh
Priority to KR1020107020291A priority patent/KR101165652B1/ko
Publication of WO2009116302A1 publication Critical patent/WO2009116302A1/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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/08—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 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
    • 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
    • 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
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/04—Insulators
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a flame retardant polyester resin composition and a flame retardant laminate having flame retardancy, mechanical properties, and heat resistance. Specifically, for example, a flexible flat cable, an electrical insulating material, a membrane, and the like.
  • the present invention relates to a flame retardant polyester resin composition and a flame retardant laminate that can be suitably used for a switch circuit printing substrate, a copier internal member, a sheet heating element substrate, an FPC (flexible printed circuit) reinforcing plate, and the like.
  • Polyester resins with excellent insulation and flexibility are attracting attention as alternative materials for vinyl chloride resins.
  • polyester resins are generally easy to burn, so it is difficult to make these resins flame-retardant. It is necessary to add flame retardant to make it flame retardant.
  • halogen flame retardants such as decabromodiphenyl ether and hexabromodiphenyl have been used.
  • Halogen flame retardants generate harmful gases such as dioxins during combustion.
  • it is also a problem in terms of safety during waste incineration and thermal recycling.
  • Phosphorus compounds are also conceivable, but not only are there problems in terms of safety and environmental harmony, but especially when a phosphorus compound is added to a polyester resin, the heat resistance decreases due to plasticization, and the molded product of the phosphorus compound. Since bleeding to the surface occurs, it cannot be said to be a practically preferable technique.
  • nitrogen compounds particularly melamine
  • non-halogen / non-phosphorus flame retardants used in polyester resins.
  • nitrogen-based compounds, particularly melamine as a flame retardant, for example, JP-A-54-12958, JP-B-60-33850, JP-B-59-50184, JP-B-62-39174 It is described in.
  • the flame retardant laminate as a known one, a laminated film having a polyester resin as an inner layer and heat resistant resin layers having an imidization ratio of 50% or more made of polyamic acid on both outer layers is disclosed. (JP 2000-280427 A, JP 2004-243760 A).
  • melamine as a flame retardant in a specific polyester resin to prepare a flame retardant polyester resin composition
  • melamine may be decomposed during molding to cause defective molding.
  • the present invention intends to provide a new flame retardant polyester resin composition that can maintain the mechanical properties and heat resistance of the polyester resin.
  • the present invention is a flame retardant polyester resin composition containing a mixture of a polyester resin having a glass transition temperature Tg of 40 ° C. or lower and a crystal melting temperature Tm of 140 ° C. to 190 ° C. and melamine. Then, a flame retardant polyester resin composition is proposed, wherein the ratio of melamine in the flame retardant polyester resin composition is 20 to 60% by mass.
  • Polyester resins having a glass transition temperature Tg of 40 ° C. or lower and a crystal melting temperature Tm of 140 ° C. to 190 ° C. have a lower melting point than ordinary polyester resins such as PET and PBT, and melamine decomposes. Since molding is possible at a temperature lower than the temperature, it is possible to eliminate the occurrence of molding defects due to decomposition of melamine during molding. In addition, excellent flexibility and mechanical properties can be obtained. By adding melamine to such a specific polyester-based resin, the added amount is lower than that of the inorganic flame retardants that have been studied so far, without impairing the inherent properties of the polyester-based resin. Flame retardancy, mechanical properties, and heat resistance can be obtained.
  • Example and comparative example of a 4th flame retardant laminated body it is explanatory drawing explaining the measuring method of the peeling strength between A layer and tin plating copper foil performed as evaluation of peeling strength with a tin plating copper foil. .
  • first flame-retardant resin composition The flame-retardant polyester resin composition according to the first embodiment (hereinafter referred to as “first flame-retardant resin composition”) will be described.
  • the first flame retardant resin composition is a flame retardant polyester resin composition containing a mixture of a polyester resin (1-A) and melamine, and preferably further contains a polyester resin (1-B). It is a flame retardant polyester resin composition.
  • the polyester resin (1-A) is a polyester resin that is a polycondensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol.
  • the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid and the like.
  • Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, polyoxylene glycol, polytetramethylene ether glycol and the like.
  • a co-polymer comprising at least one polycarboxylic acid component selected from terephthalic acid, isophthalic acid, and adipic acid and at least one polyhydric alcohol component selected from 1,4-butanediol and ethylene glycol. It is preferably a coalescence.
  • the proportion of terephthalic acid in the polyvalent carboxylic acid component is preferably 50 to 90 mol%.
  • the polyester resin (1-A) having such a composition has a lower melting point than general polyester resins such as PET and PBT, and can be molded at a temperature lower than the temperature at which melamine starts to decompose. Therefore, it is possible to eliminate the occurrence of molding defects due to decomposition of melamine during molding. In addition, excellent flexibility and mechanical properties can be obtained.
  • the polyester resin (1-A) preferably contains terephthalic acid as a polyvalent carboxylic acid component in an amount of 55 mol% or more, particularly 60 mol% or more, and more preferably 85 mol% or less, particularly 80 mol% or less. More preferably. However, it is not intended to limit the polyester resin in which the proportion of terephthalic acid in the polyvalent carboxylic acid component is 50 to 90 mol%.
  • the polyester resin (1-A) preferably contains 70 to 100 mol% of the total proportion of 1,4-butanediol and ethylene glycol in the polyhydric alcohol component. With the polyester resin (1-A) having such a composition, excellent flexibility, mechanical properties, and heat resistance can be obtained. From this point of view, the polyester resin (1-A) contains 1,4-butanediol and ethylene glycol as a polyhydric alcohol component in a total amount of 75 mol% or more, particularly preferably 80 mol% or more, and preferably 100 mol%. Is more preferable. However, the polyhydric alcohol component may include any one of 1,4-butanediol, ethylene glycol, and diethylene glycol, or may include two or more.
  • the glass transition temperature Tg of the polyester resin (1-A) is preferably 40 ° C. or lower, and particularly preferably ⁇ 20 to 40 ° C.
  • a flame retardant polyester resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared.
  • the Tg of the polyester-based resin (1-A) is particularly preferably ⁇ 15 ° C. or higher, more preferably ⁇ 10 ° C. or higher, and particularly preferably 35 ° C. or lower, especially 30 ° C. or lower.
  • the crystal melting temperature Tm of the polyester resin (1-A) is preferably 140 to 190 ° C. If the crystal melting temperature Tm of the polyester resin (1-A) is within such a range, a flame-retardant polyester resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared. From this viewpoint, the Tm of the polyester-based resin (1-A) is particularly preferably 145 ° C. or higher, particularly 150 ° C. or higher, and particularly preferably 185 ° C. or lower, especially 180 ° C. or lower.
  • the crystal melting heat ⁇ Hm of the polyester resin (1-A) is preferably 20 to 40 J / g.
  • ⁇ Hm of the polyester resin (1-A) is within such a range, a flame-retardant polyester resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared.
  • the ⁇ Hm of the polyester-based resin (1-A) is particularly preferably 22 J / g or more, more preferably 25 J / g or more, and particularly 38 J / g or less, particularly 35 J / g or less. preferable.
  • the mass average molecular weight of the polyester resin (1-A) is preferably 10,000 to 300,000. If the mass average molecular weight of the polyester-based resin (1-A) is within such a range, flexibility can be obtained, and the melt viscosity is appropriate, so that there is little possibility of problems in molding. From this point of view, the mass average molecular weight of the polyester-based resin (1-A) is particularly preferably 20,000 or more, more preferably 30,000 or more, particularly 200,000 or less, especially 150,000 or less. More preferably.
  • the mass average molecular weight can be measured by the following method. The same applies to other resins. Using gel permeation chromatography, measurement is made at a solvent chloroform, a solution concentration of 0.2 wt / vol%, a solution injection amount of 200 ⁇ L, a solvent flow rate of 1.0 ml / min, a solvent temperature of 40 ° C., and a mass average molecular weight in terms of polystyrene is obtained. Can be calculated.
  • the mass average molecular weight of the standard polystyrene used in this case is 2,000,000, 430,000, 110,000, 35,000, 10,000, 40,00, 600.
  • polyester resin (1-B) is a polyester resin that is a polycondensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol.
  • polyvalent carboxylic acid examples include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid and the like.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, polyoxylene glycol, polytetramethylene ether glycol and the like.
  • a co-polymer comprising at least one polycarboxylic acid component selected from terephthalic acid, isophthalic acid, and adipic acid and at least one polyhydric alcohol component selected from 1,4-butanediol and ethylene glycol. It is preferably a coalescence.
  • the proportion of terephthalic acid in the polyvalent carboxylic acid component is preferably 20 mol% or more and less than 70 mol%. It is preferable to blend the polyester-based resin (1-B) having such a composition with the polyester-based resin (1-A) because flexibility and particularly excellent elongation can be obtained. From this point of view, the polyester resin (1-B) further preferably contains terephthalic acid as a polyvalent carboxylic acid component in an amount of 30 mol% or more, particularly 40 mol% or more, and less than 65 mol%, particularly less than 60 mol%. More preferably. However, it is not intended to limit the polyester-based resin in which the proportion of terephthalic acid in the polyvalent carboxylic acid component is 20 mol% or more and less than 70 mol%.
  • the total proportion of 1,4-butanediol and ethylene glycol in the polyhydric alcohol component is preferably 65 to 100 mol%.
  • the polyester resin (1-B) preferably contains a total of 1,4-butanediol and ethylene glycol as polyhydric alcohol components of 70 mol% or more, particularly 75 mol% or more, and particularly 95 mol%. % Or less, more preferably 90 mol%.
  • the polyhydric alcohol component may include any one of 1,4-butanediol, ethylene glycol, and diethylene glycol, or may include two or more.
  • the glass transition temperature Tg of the polyester resin (1-B) is preferably ⁇ 100 or higher and lower than ⁇ 20 ° C.
  • the flexibility, particularly the elongation can be increased by blending with the polyester resin (1-A), and the effect is 200 ⁇ m in thickness. This is particularly effective for the following thin films.
  • the polyester resin (1-B) has a temperature of ⁇ 90 ° C. or higher, preferably ⁇ 80 ° C. or higher, and is preferably lower than ⁇ 25 ° C., and more preferably lower than ⁇ 30 ° C.
  • the crystal melting temperature Tm of the polyester resin (1-B) is preferably 100 ° C. or higher and lower than 140 ° C. If the crystal melting temperature Tm of the polyester resin (1-B) is within such a range, a flame retardant polyester resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared. From this viewpoint, the Tm of the polyester-based resin (1-B) is particularly preferably 105 ° C. or higher, particularly preferably 110 ° C. or higher, and particularly preferably lower than 135 ° C., particularly preferably lower than 130 ° C.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (1-B) is preferably 1 J / g or more and less than 20 J / g. If the ⁇ Hm of the polyester resin (1-B) is within such a range, the mechanical properties, particularly elongation and flexibility of the flame retardant polyester resin composition can be further improved. From this viewpoint, the ⁇ Hm of the polyester resin (1-B) is particularly preferably 5 J / g or more, particularly preferably 10 J / g or more, and particularly preferably less than 18 J / g, particularly less than 15 J / g. preferable.
  • the mass average molecular weight of the polyester resin (1-B) is preferably 10,000 to 300,000. If the mass average molecular weight of the polyester-based resin (1-B) is within such a range, flexibility can be obtained, and the melt viscosity is appropriate, so that there is little possibility of problems in molding. From this viewpoint, the mass average molecular weight of the polyester-based resin (1-B) is particularly preferably 20,000 or more, more preferably 30,000 or more, particularly 200,000 or less, especially 150,000 or less. More preferably.
  • the mass average molecular weight can be measured by the following method. The same applies to other resins. Using gel permeation chromatography, measurement is made at a solvent chloroform, a solution concentration of 0.2 wt / vol%, a solution injection amount of 200 ⁇ L, a solvent flow rate of 1.0 ml / min, a solvent temperature of 40 ° C., and a mass average molecular weight in terms of polystyrene is obtained. Can be calculated.
  • the mass average molecular weight of the standard polystyrene used in this case is 20000, 430000, 110000, 35000, 10000, 4000, 600.
  • (melamine) Melamine is a kind of organic nitrogen compound having a triazine ring at the center of the structure, and examples thereof include 2,4,6-triamino-1,3,5-triazine. Since melamine generates nonflammable gas at the time of combustion, the first flame retardant resin composition can be made flame retardant. Melamine has a lower decomposition initiation temperature than melamine derivatives (for example, melamine cyanurate, melamine phosphate, etc.) and has no carbonization promoting action, so it is generally difficult to use as a flame retardant.
  • melamine derivatives for example, melamine cyanurate, melamine phosphate, etc.
  • polyester resin (1-A) or the polyester resins (1-A) and (1-B) of the present invention can be melt-kneaded at a temperature lower than the decomposition start temperature of melamine, and At the time of combustion, melamine is decomposed prior to the decomposition of the resin, so that excellent flame retardancy can be imparted by the endothermic action during sublimation and generation of inert gas.
  • the average particle size of melamine is preferably 10 ⁇ m or less, particularly 0.5 ⁇ m to 10 ⁇ m. If the average particle size of the melamine is within this range, the melamine does not agglomerate and is uniformly dispersed in the resin composition. Therefore, the flame retardancy is not impaired without impairing the mechanical strength of the first flame retardant resin composition. Can be improved. From this point of view, the average particle size of melamine is particularly preferably 1.0 ⁇ m or more, particularly preferably 1.5 ⁇ m or more, particularly preferably 8.0 ⁇ m or less, and particularly preferably 6.0 ⁇ m or less. The average particle diameter is a value calculated by using melamine as the equivalent circle diameter.
  • a surface treatment can be applied to melamine as long as the effects of the present invention are not impaired.
  • Specific examples of the surface treatment include surface treatment using a silane coupling agent such as epoxy silane, vinyl silane, methacryl silane, amino silane, isocyanate silane, titanate coupling agent, higher fatty acid and the like.
  • melamine and other flame retardants or flame retardant aids may be used in combination as long as the effects of the present invention are not impaired.
  • flame retardants include, for example, phosphoric acid esters, phosphoric acid ester amides, condensed phosphoric acid esters, phosphazene compounds, phosphorus compounds such as polyphosphates, aluminum hydroxide, magnesium hydroxide, calcium aluminate water Examples thereof include metal hydroxides such as hydrates and tin oxide hydrates.
  • flame retardant aids include, for example, metal compounds such as zinc stannate, zinc borate, iron nitrate, copper nitrate, and sulfonic acid metal salts, silicone compounds such as dimethyl silicone, phenyl silicone, and fluorine silicone, polytetrafluoro Fluorine compounds such as ethylene can be mentioned.
  • metal compounds such as zinc stannate, zinc borate, iron nitrate, copper nitrate, and sulfonic acid metal salts
  • silicone compounds such as dimethyl silicone, phenyl silicone, and fluorine silicone, polytetrafluoro Fluorine compounds such as ethylene can be mentioned.
  • the blending ratio of melamine in the first flame retardant resin composition is preferably 20 to 60% by mass. If the blending ratio of melamine in the first flame-retardant resin composition is 20% by mass or more, sufficient flame retardancy can be obtained, while if the blending ratio of melamine is 60% by mass or less, the machine There is no loss of physical properties. From such a viewpoint, the blending ratio of melamine in the first flame retardant resin composition is particularly preferably 20% by mass or more, and more preferably 30% by mass or more. Moreover, it is especially preferable that it is 50 mass% or less, and it is still more preferable that it is 40 mass% or less especially.
  • the mixing ratio of the polyester resin (1-A) and the polyester resin (1-B) is 90:10 to 30:70 by mass ratio. Is preferred. With such a ratio, the mechanical properties can be further improved without impairing the heat resistance of the polyester resin (1-A).
  • the mixing ratio of the polyester resin (1-A) and the polyester resin (1-B) is 80:20 or more, particularly 70:30 or more, particularly the polyester resin (1-B).
  • the polyester resin (1-B) is preferably mixed as described above, while the polyester resin (1-B) is contained in a ratio of 40:60 or less, particularly 50:50 or less. -B) is preferably mixed.
  • a carbodiimide compound may be blended with the first flame-retardant resin composition in order to impart hydrolysis resistance. However, it is not necessary to mix.
  • bis (dipropylphenyl) carbodiimide poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropyl) Phenylene carbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide) and the like, and monomers thereof.
  • the carbodiimide compound is used alone or in combination of two or more.
  • the amount of the carbodiimide compound is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the first flame retardant resin composition.
  • the blending amount of the carbodiimide compound is more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, with respect to 100 parts by mass of the first flame retardant resin composition. .
  • the first flame retardant resin composition may contain additives such as a heat stabilizer, an antioxidant, a UV absorber, a plasticizer, a nucleating agent, a light stabilizer, a pigment, and a dye as necessary. it can.
  • the first flame retardant resin composition can be prepared to have flame retardancy, flexibility, mechanical properties, and heat resistance. More specifically, regarding the flame retardancy, flame retardancy satisfying the VTM-0 standard can be obtained in the UL94 vertical combustion test defined by Underwriters Laboratories.
  • the mechanical properties when the tensile strength at break is measured based on JIS C 2318, the tensile strength can be adjusted to 10 MPa or more, preferably 15 MPa or more.
  • the tensile elongation at break is measured according to JIS C 2318, the tensile elongation can be adjusted to 10% or more, preferably 20% or more.
  • heat resistance when the crystal melting heat quantity ⁇ Hm is measured based on JIS K7121, the crystal melting heat quantity ( ⁇ Hm) can be adjusted to 1 J / g or more, preferably 3 J / g or more.
  • the first flame retardant resin composition can be formed into a flame retardant resin body such as a film, a sheet, a plate, or an injection molded product.
  • raw materials such as polyester resin (1-A) and melamine and, if necessary, other resins and additives such as polyester resin (1-B) are directly mixed, and an extruder or injection molding machine.
  • the raw material is melt-mixed using a twin screw extruder, extruded into a strand shape to create a pellet, and then the pellet is put into an extruder or an injection molding machine.
  • a method of molding can be mentioned. In any method, it is necessary to consider a decrease in molecular weight due to hydrolysis of the polyester-based resin, and the latter is preferably selected for uniform mixing. Therefore, the latter manufacturing method will be described below.
  • the polyester resin (1-A) and melamine, and if necessary, other resins and additives such as the polyester resin (1-B) are sufficiently dried to remove moisture, and then used with a twin screw extruder. It is melt mixed and extruded into a strand shape to produce pellets.
  • the melting point changes depending on the composition ratio of the polyester resins (1-A) and (1-B), for example, the content ratio of terephthalic acid, and that the viscosity changes depending on the mixing ratio of each raw material.
  • the melt extrusion temperature is preferably adjusted to a temperature range of 160 ° C. or higher and 220 ° C. or lower, particularly less than 210 ° C.
  • a film, a sheet, a plate, or an injection molded product can be molded by the following method.
  • sheet and plate molding methods roll stretching, tenter stretching, tubular and inflation methods, as well as sheet and plate molding methods such as general T-die casting and pressing can be adopted. it can.
  • the molding method of the injection molded body is not particularly limited, and for example, an injection molding method such as a general injection molding method for a thermoplastic resin, a gas assist molding method, and an injection compression molding method can be employed.
  • an injection molding method such as a general injection molding method for a thermoplastic resin, a gas assist molding method, and an injection compression molding method can be employed.
  • an in-mold molding method, a gas press molding method, a two-color molding method, a sandwich molding method, PUSH-PULL, SCORIM, or the like can also be employed according to other purposes.
  • the laminated body can also be formed by providing one or more layers not containing a flame retardant on one side or both sides of the layer made of the first flame retardant resin composition.
  • the layer containing no flame retardant is not particularly limited.
  • a layer made of the stretched polyethylene terephthalate film or the like is formed. Is preferred.
  • adhesive layer made of rubber, acrylic, vinyl ether or other solvent type or emulsion type adhesives Is preferably formed.
  • the ratio of the thickness of the layer made of the flame-retardant polyester resin composition to the total thickness of the laminate is preferably 20 to 95%.
  • the ratio of the thickness of the layer composed of the flame-retardant polyester resin composition in the total thickness of the laminate is particularly preferably 30% or more, and particularly preferably 40% or more, and 80%. It is particularly preferable that the ratio is 70% or less.
  • the layers can be laminated by coextrusion, extrusion lamination, heat lamination, dry lamination, or the like.
  • the laminate obtained in the above step can be stretched uniaxially or biaxially using a roll method, a tenter method, a tubular method, or the like.
  • a layer made of a polyester resin (A) is extruded from a T die, I die, etc. using a single screw or twin screw extruder, and then a roll method, a tenter method, a tubular method, etc. To obtain a monolayer. Subsequently, a laminate can be obtained by laminating a layer containing no flame retardant on one side or both sides of the obtained layer.
  • a layer made of a polyester resin (1-A) is extruded from a T die, I die or the like using a single screw or twin screw extruder to obtain a single layer body. Moreover, the layer which does not contain a flame retardant is produced using the same method. Subsequently, these layers are laminated by heating or by disposing an adhesive layer between the layers, whereby a laminate can be obtained.
  • the first flame retardant resin composition has excellent flame retardancy, mechanical properties, flexibility, and heat resistance, so it can be used for cellular phone parts, cable coating materials, packings, electrical insulation films and sheets, flats. It can be widely used in the fields of home appliances such as cable materials and vibration damping materials, as well as adhesive tape base materials, rolls, water shielding sheets, gaskets, anti-slip materials, wire clothing materials, and other building materials and industrial applications. In addition, since it does not contain a halogen compound or a phosphorus compound, it is possible to provide a material with excellent safety that does not cause problems such as environmental pollution.
  • Second flame-retardant resin composition The flame-retardant polyester resin composition according to the second embodiment (hereinafter referred to as “second flame-retardant resin composition”) will be described.
  • the second flame retardant resin composition is a flame retardant polyester resin composition containing a mixture of a polyester resin (2-A), melamine, and a phenoxy resin.
  • A) contains 50 to 90 mol% of terephthalic acid as the polyvalent carboxylic acid component and 70 to 100 mol% in total of 1,4-butanediol, ethylene glycol and diethylene glycol as the polyhydric alcohol component
  • the second feature is that the proportion of melamine in the flame-retardant polyester resin composition is 10 to 60% by mass and the proportion of phenoxy resin is 1 to 25% by mass. It is a flame retardant polyester resin composition.
  • Polyester resin containing 50 to 90 mol% terephthalic acid as the polyvalent carboxylic acid component and 70 to 100 mol% in total of 1,4-butanediol, ethylene glycol and diethylene glycol as the polyhydric alcohol component (2-A) has a lower melting point than general polyester resins such as PET and PBT, and can be molded at a temperature lower than the temperature at which melamine decomposes. It is possible to eliminate the occurrence of defects. In addition, excellent flexibility and mechanical properties can be obtained. By blending melamine with the specific polyester resin (2-A) having such excellent flexibility and mechanical properties, inorganic materials that have been studied in the past without impairing the inherent properties of the polyester resin.
  • the addition amount is lower than that of the system flame retardant, and excellent flame retardancy can be imparted.
  • the phenoxy resin is completely compatible with the specific polyester resin (2-A)
  • the cohesive phenoxy resin can be finely dispersed in the polyester resin, and excellent stress relaxation characteristics can be obtained. Can do.
  • phenoxy resin since phenoxy resin has the property of being easily carbonized, the carbonization promoting effect of phenoxy resin and the combustion effect of melamine work synergistically, further improving flame retardancy while suppressing the amount of melamine compounded. Can be made. Details will be described below.
  • the second flame retardant resin composition is a flame retardant polyester resin composition containing a mixture of polyester resin (2-A), melamine, and phenoxy resin.
  • the polyester resin (2-A) is a resin composition mainly composed of a polyester resin (2-A) which is a polycondensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol.
  • -A) contains 50 to 90 mol% of terephthalic acid as the polyvalent carboxylic acid component, and 70 to 100 mol in total of 1,4-butanediol, ethylene glycol, and diethylene glycol as the polyhydric alcohol component It is preferable to use a polyester resin.
  • the resin composition mainly composed of the polyester resin (2-A) having such a composition has a melting point lower than that of general polyester resins such as PET and PBT, and is lower than the temperature at which melamine decomposes. Since molding is possible in the region, it is possible to eliminate the occurrence of molding defects due to decomposition of melamine during molding. In addition, excellent flexibility and mechanical properties can be obtained. From this point of view, the polyester resin (2-A) preferably contains terephthalic acid as a polyvalent carboxylic acid component in an amount of 55 mol% or more, particularly 60 mol% or more, more preferably 85 mol% or less, particularly 80 mol% or less. Is more preferable.
  • 1,4-butanediol, ethylene glycol and diethylene glycol are contained in a total amount of 75 mol% or more, particularly preferably 80 mol% or more, and more preferably 100 mol%.
  • the polyhydric alcohol component may include any one of 1,4-butanediol, ethylene glycol, and diethylene glycol, or may include two or more.
  • the polyester resin (2-A) is a polyvalent carboxylic acid, in addition to terephthalic acid, for example, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid and other polyvalent carboxylic acids. Or 2 or more types may be included.
  • terephthalic acid for example, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid and other polyvalent carboxylic acids.
  • 1,4-butanediol ethylene glycol and diethylene glycol as polyhydric alcohols, for example, propylene glycol, 1,6-hexanediol, cyclohexanediol, polyoxylene glycol, polytetramethylene ether glycol and other polyvalent alcohols.
  • One kind or two or more kinds of alcohols may be contained.
  • polyester resin (2-A) It is also possible to use a commercially available polyester resin as the polyester resin (2-A).
  • a commercially available polyester resin for example, “Byron” series manufactured by Toyobo Co., Ltd., “Nichigo Polyester” series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. and the like can be mentioned, and these can be used alone or in combination of two or more.
  • the polyester resin (2-A) may be a polyester resin mainly composed of a mixture of two or more polyester resins.
  • the polycarboxylic acid component contains isophthalic acid in a proportion of 30 mol% to 50 mol%
  • the polyhydric alcohol component contains ethylene glycol in a proportion of 50 mol% to 100 mol%.
  • a mixture with the polyester resin (a-2) is a particularly preferred example.
  • polyester resin (a-1) and (a-2) as a main component of polyester resin (2-A), a resin composition having excellent mechanical properties and flexibility can be provided. it can. In particular, by blending the polyester resin (a-2), flexibility, particularly ease of elongation, can be enhanced.
  • the content ratio of isophthalic acid in the polyvalent carboxylic acid component in the polyester resin (a-1) is more preferably 7 mol% or more, particularly preferably 10 mol% or more, less than 25 mol%, particularly less than 20 mol%. More preferably. Further, the content ratio of ethylene glycol in the polyhydric alcohol component in the polyester resin (a-1) is more preferably 5 mol% or more, particularly preferably 10 mol% or more, and less than 45 mol%, particularly less than 40 mol%. Is more preferable.
  • the content ratio of isophthalic acid in the polyvalent carboxylic acid component in the polyester-based resin (a-2) is more preferably 33 mol% or more, particularly 35 mol% or more, and more preferably 43 mol% or less, particularly 40 mol% or less. Further preferred. Further, the content ratio of ethylene glycol in the polyhydric alcohol component in the polyester resin (a-2) is more preferably 55 mol% or more, particularly preferably 60 mol% or more, and 90 mol% or less, particularly 80 mol% or less. Is more preferable.
  • the mass average molecular weight of the polyester resin (2-A) (in the case of two types, the average thereof) is preferably 10,000 to 300,000. If the mass average molecular weight of the polyester-based resin (2-A) is within such a range, flexibility can be obtained, and the melt viscosity is appropriate, so that there is little possibility of problems in molding. From this viewpoint, the mass average molecular weight of the polyester-based resin (2-A) is particularly preferably 20,000 or more, more preferably 30,000 or more, particularly 200,000 or less, especially 150,000 or less. More preferably.
  • the mass average molecular weight can be measured by the following method. The same applies to other resins. Using gel permeation chromatography, measurement is made at a solvent chloroform, a solution concentration of 0.2 wt / vol%, a solution injection amount of 200 ⁇ L, a solvent flow rate of 1.0 ml / min, a solvent temperature of 40 ° C., and a mass average molecular weight in terms of polystyrene is obtained. Can be calculated.
  • the mass average molecular weight of the standard polystyrene used in this case is 20000, 430000, 110000, 35000, 10000, 4000, 600.
  • the glass transition temperature Tg of the polyester resin (2-A) is preferably -100 ° C to 40 ° C.
  • a flame retardant polyester resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared.
  • the Tg of the polyester resin (2-A) is particularly preferably ⁇ 90 ° C. or higher, particularly preferably ⁇ 80 ° C. or higher, particularly 35 ° C. or lower, and particularly preferably 30 ° C. or lower.
  • the crystal melting temperature Tm of the polyester resin (2-A) is preferably 100 ° C. to 190 ° C. If the Tm of the polyester resin (2-A) is within such a temperature range, a flame-retardant polyester resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared. From this point of view, the Tm of the polyester resin (2-A) is particularly preferably 105 ° C. or higher, particularly preferably 110 ° C. or higher, and is preferably 185 ° C. or lower, particularly 180 ° C. or lower.
  • the crystal melting heat ⁇ Hm of the polyester resin (2-A) is preferably 1 J / g to 30 J / g. If ⁇ Hm of the polyester resin (2-A) is within such a temperature range, a flame-retardant polyester resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared. From this viewpoint, the ⁇ Hm of the polyester-based resin (2-A) is particularly preferably 5 J / g or more, particularly preferably 10 J / g or more, particularly 28 J / g or less, particularly 25 J / g or less. preferable.
  • melamine Melamine is similar to the melamine used in the first flame retardant resin composition, and can obtain the same action. Similarly to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination as long as the effects of the present invention are not impaired.
  • the phenoxy resin is a resin obtained by a reaction between an aromatic dihydric phenol compound such as bisphenol A and epichlorohydrin. Since the phenoxy resin is completely compatible with the specific polyester resin (2-A), the cohesive phenoxy resin can be finely dispersed in the polyester resin (2-A). Stress relaxation characteristics can be obtained. Moreover, since the phenoxy resin has the property of being easily carbonized, it works synergistically with the combustion effect of melamine, reducing the amount of melamine added and reducing the flame retardancy of the second flame retardant resin composition. This can be further improved.
  • Phenoxy resins used include hydroquinone, resorcin, 4,4′-bisphenol, 4,4′-dihydroxydiphenyl ether, bisphenol A, bisphenol F, and aromatic dihydroxy compounds such as 2,6-dihydroxynaphthalene, ethylene glycol diglycidyl
  • aromatic dihydroxy compounds such as 2,6-dihydroxynaphthalene, ethylene glycol diglycidyl
  • One or more compounds selected from aliphatic dihydroxy compounds such as ether propylene glycol diglycidyl ether, neopentyl glycol, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Examples thereof include polyhydroxy polyether obtained by condensing with epichlorohydrin.
  • phenoxy resins include Epicoat (registered trademark) E1256, E4250, E4275 manufactured by Japan Epoxy Resin Co., Ltd., PKHH, PKHC, PKHJ, PKHB, PKFE manufactured by InChem.
  • Epicoat (registered trademark) E4275 made by Japan Epoxy Resin Co., Ltd., whose main component is bisphenol F, is particularly preferable.
  • the blending ratio of melamine in the second flame retardant resin composition is preferably 10 to 60% by mass. If the blending ratio of melamine in the second flame-retardant resin composition is 10% by mass or more, sufficient flame retardancy can be obtained, while if the blending ratio of melamine is 60% by mass or less, the machine There is no loss of physical properties. From such a viewpoint, the blending ratio of melamine in the second flame retardant resin composition is particularly preferably 20% by mass or more, and more preferably 30% by mass or more. Moreover, it is especially preferable that it is 50 mass% or less, and it is still more preferable that it is 40 mass% or less especially.
  • the blending ratio of the phenoxy resin in the second flame retardant resin composition is preferably 1 to 25% by mass.
  • the ratio of the phenoxy resin in the second flame retardant resin composition is preferably 2% by mass or more, and more preferably 5% by mass or more.
  • the glass transition temperature Tg of the polyester resin (2-A) is adjusted to 40 to 50 ° C. by blending the phenoxy resin. Is preferred.
  • a carbodiimide compound may be blended with the second flame retardant resin composition in order to impart hydrolysis resistance. However, it is not necessary to mix.
  • blend are the same as the carbodiimide compound to mix
  • additives such as a heat stabilizer, an antioxidant, a UV absorber, a plasticizer, a nucleating agent, a light stabilizer, a pigment, and a dye may be blended as necessary. it can.
  • the second flame retardant resin composition can have flame retardancy, flexibility, mechanical properties, and stress relaxation properties, and can be further prepared with heat resistance. More specifically, regarding the flame retardancy, flame retardancy satisfying the VTM-0 standard can be obtained in the UL94 vertical combustion test defined by Underwriters Laboratories.
  • the mechanical properties when the tensile strength at break is measured based on JIS C 2318, the tensile strength can be adjusted to 10 MPa or more, preferably 15 MPa or more.
  • the tensile elongation at break is measured according to JIS C 2318, the tensile elongation can be adjusted to 10% or more, preferably 20% or more.
  • the stress relaxation rate when the stress relaxation rate is measured based on JIS C 2318, the stress relaxation rate can be adjusted to 50% or more, preferably 55% or more.
  • the crystal melting heat quantity ( ⁇ Hm) when the crystal melting heat quantity ( ⁇ Hm) is measured based on JIS K7121, the crystal melting heat quantity ( ⁇ Hm) can be adjusted to 1 J / g or more, preferably 5 J / g or more.
  • the second flame retardant resin composition can be formed into a flame retardant resin body such as a film, a sheet, a plate, or an injection molded product.
  • the specific molding method at that time is the same as that of the first flame-retardant resin composition.
  • the second flame retardant resin composition has excellent flame retardancy, mechanical properties, and flexibility, so that it can be used for cellular phone parts, cable coating materials, packings, films and sheets for electrical insulation, and flat cable materials. It can be widely used for household appliances such as vibration damping materials, and for fields such as adhesive tape base materials, rolls, water shielding sheets, gaskets, anti-slip materials, wire clothing materials, and other building materials and industrial applications.
  • the second flame retardant resin composition since it does not contain a halogen compound or a phosphorus compound, it is possible to provide a material with excellent safety that does not cause problems such as environmental pollution.
  • the second flame retardant resin composition since the second flame retardant resin composition has excellent stress relaxation properties, the second flame retardant resin composition is particularly excellent as a substitute material for a so-called vinyl tape, particularly as a substitute material for the flame retardant vinyl tape.
  • the third flame retardant laminate has an A and a main component of a mixture of a polyester resin (3-A) having a glass transition temperature of 30 ° C. or less and a heat of crystal fusion ⁇ Hm of 40 J / g or less and melamine.
  • “on one surface” means that the B layer is provided directly on the surface of the A layer, and that another layer that is a single layer or a multilayer is provided on the surface of the A layer. This means that the B layer is provided on the top.
  • the B layer not containing a flame retardant is particularly laminated on one side or both sides. Even in this case, it is possible to exhibit excellent flame retardancy as a whole laminate.
  • a halogen-based compound and a phosphorus compound are not contained, it is possible to provide a material having excellent safety without causing problems such as environmental pollution.
  • the A layer of the third flame retardant laminate is a layer mainly composed of a polyester resin (3-A) and melamine.
  • polyester resin (3-A) It is important that the polyester resin (3-A) used in the third flame-retardant laminate has a glass transition temperature of 30 ° C. or lower and a crystal melting heat ⁇ Hm of 40 J / g or lower. By satisfying this condition, it is possible to provide a laminate that has good adhesion to the polyester resin (3-B) and does not cause separation between layers during secondary processing and use. . Further, the polyester resin (3-A) in the third flame-retardant laminate may be a single resin or a mixture of two or more kinds of resins. Specific examples of the polyester resin (3-A) include aliphatic polyesters such as aromatic polyester lactic acid resins obtained by polymerizing polyvalent carboxylic acids and polyhydric alcohols.
  • the glass transition temperature of the polyester resin (3-A) used for the third flame retardant laminate is 30 ° C. or lower, preferably 20 ° C. or lower, more preferably 10 ° C. or lower.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (3-A) used for the third flame retardant laminate is 40 J / g or less, preferably 25 J / g or less, and more preferably 20 J / g or less. If the glass transition temperature of the polyester resin (3-A) is 30 ° C. or less and the heat of crystal fusion ⁇ Hm is 40 J / g or less, the polyester resin (3- The problem of peeling with B) does not occur.
  • the lower limit value of the glass transition temperature of the polyester resin (3-A) used in the third flame-retardant laminate and the lower limit value of the crystal melting heat amount ⁇ Hm are not particularly limited, but the glass transition temperature is not limited. Is -100 ° C. or higher, and the heat of crystal fusion ⁇ Hm is 0 J / g or higher, excellent adhesive strength with the polyester resin (3-B) can be obtained in all practical temperature ranges.
  • polyester resin (3-A) examples include aliphatic polyesters, aromatic aliphatic polyesters having a glass transition temperature of 30 ° C. or lower and a crystal melting heat ⁇ Hm of 40 J / g or lower, or polyester hot A melt adhesive or the like can be used alone or by mixing.
  • Examples of the polyvalent carboxylic acid component used in the aliphatic or aromatic polyester obtained by polymerizing the polyvalent carboxylic acid and the polyhydric alcohol include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5- Dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis Aromatic dicarboxylic such as (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid Acid, succinic acid, adipic acid,
  • polyhydric alcohol component examples include diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans-tetramethyl-1, 3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples include 4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), and the like. It is done.
  • These polyhydric alcohol components can be used individually by 1
  • a polybutylene succinate-adipate copolymer obtained by polymerizing succinic acid, 1,4-butanediol, and adipic acid "GSPla (registered trademark)” AD series, "Bionore (registered trademark)” # 3000 series manufactured by Showa Polymer Co., Ltd.) and the like.
  • the aromatic aliphatic polyester used for the third flame retardant laminate is a polybutylene adipate / terephthalate copolymer (BASF), obtained by polymerizing adipic acid, 1,4-butanediol, and terephthalic acid.
  • BASF polybutylene adipate / terephthalate copolymer
  • the weight average molecular weight of the aliphatic polyester and aromatic aliphatic polyester is usually 50,000 or more, preferably 80,000 or more, more preferably 100,000 or more, and the weight average molecular weight of the aromatic aliphatic polyester is usually 400,000 or less, preferably 300,000 or less, more preferably 250,000 or less.
  • the weight average molecular weight of the aromatic aliphatic polyester is 50,000 or more, the mechanical properties during use are not deteriorated, and the weight average molecular weight of the aromatic aliphatic polyester is 400,000 or less. Therefore, the viscosity at the time of processing becomes optimum, and the problem of poor thickness of the laminate or poor dispersion of melamine does not occur.
  • the weight average molecular weight can be measured by the following method. That is, using gel permeation chromatography, using chloroform as a solvent (solution concentration 0.2 wt / vol%, solution injection amount 200 ⁇ l, solvent flow rate 1.0 ml / min, solvent temperature 40 ° C.)
  • the weight average molecular weight of the polyester resin was calculated in terms of polystyrene.
  • the weight average molecular weight of the standard polystyrene used is 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, 600.
  • polyester hot melt adhesive used for the third flame retardant laminate
  • a resin composition containing a polyester hot melt resin which is a polycondensation polymer of dibasic acid and glycol, as a main component (manufactured by Toagosei Co., Ltd.) “Aronmelt (registered trademark) PES120L, 140H, 111E, 126E”, “Byron (registered trademark)” series manufactured by Toyobo Co., Ltd.) and the like.
  • dibasic acids used as raw material monomers for polyester hot melt adhesives include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc.
  • glycols examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol.
  • a hot melt resin made of a polyester resin containing adipic acid, 1,4-butanediol, or the like in the molecular skeleton is preferably used.
  • the polyester-based hot melt adhesive has a number average molecular weight of usually 10,000 or more, preferably 12,000 or more, more preferably 15,000 or more, and a number average molecular weight of 50,000 or less, preferably 40,000. Hereinafter, it is more preferably 24,000 or less. If the mass average molecular weight of the polyester hot melt adhesive is in the range of 10,000 or more and 50,000 or less, it has practically sufficient mechanical properties and has an appropriate melt viscosity. Less likely to cause problems.
  • melamine Melamine is similar to the melamine used in the first flame retardant resin composition, and can obtain the same action. Similarly to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination as long as the effects of the third flame retardant laminate are not impaired.
  • the content of melamine with respect to the total mass of the polyester resin (3-A) is 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and 80% by mass or less, preferably 70% by mass. % Or less, more preferably 60% by mass or less.
  • the content of melamine with respect to the total mass of the polyester resin (3-A) is 10% by mass or more, sufficient flame retardancy can be imparted.
  • the content of melamine is 80% by mass or less, the mechanical properties of the layer having no flame retardancy are not significantly lowered, and the mechanical properties of the entire laminate are not impaired.
  • the A layer of the third flame retardant laminate is mainly composed of a mixture of polyester resin A and melamine.
  • the mixture of the polyester resin A and melamine is constituted by the above-described blending ratio, and the mixture is produced by extrusion with a single screw or twin screw extruder to form the A layer.
  • B layer which comprises a 3rd flame-retardant laminated body is not specifically limited, It is possible to use the material which can comprise a well-known layer. For example, a thermoplastic resin, a metal, etc. are mentioned. However, for the purpose of imparting heat resistance, mechanical properties, and surface properties, it is preferable to use a polyester resin (3-B). In addition, if the purpose is to improve the adhesion to other materials and use it for applications such as pressure-sensitive adhesive tapes, it is possible to use rubber-type, acrylic-type, vinyl ether-type solvent-type or emulsion-type pressure-sensitive adhesives. preferable. Details will be described below.
  • thermoplastic resin used for the B layer examples include polyolefin resins such as low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene vinyl acetate copolymer, or polymethylpentene, polystyrene resins, and polyacrylic resins. And thermoplastic resins such as polyvinyl chloride, polyester resins, polyether resins and polyamide resins. Among these, the polyester-based resin is preferable in the adhesion to the A layer and the production of the laminate. In order to improve the adhesion to other materials, a solvent type such as rubber, acrylic, vinyl ether, or emulsion type pressure sensitive adhesive can be used as the B layer.
  • a solvent type such as rubber, acrylic, vinyl ether, or emulsion type pressure sensitive adhesive can be used as the B layer.
  • Examples of the metal used for the B layer include aluminum, nickel, gold, silver, copper, or any one of platinum, titanium, tantalum, and tungsten, or a mixture of plural kinds.
  • polyester resin (3-B) used for the third flame retardant laminate preferably has a glass transition temperature of 50 ° C. or higher and a crystal melting heat ⁇ Hm of 40 J / g or higher. By satisfying this condition, a laminate having excellent heat resistance can be provided.
  • Specific examples of the polyester resin (3-B) include aliphatic polyesters such as aromatic polyesters and lactic acid resins obtained by polymerizing polyvalent carboxylic acids and polyhydric alcohols.
  • the glass transition temperature of the polyester resin (3-B) used for the third flame-retardant laminate is 50 ° C. or higher, preferably 55 ° C. or higher, and more preferably 60 ° C. or higher.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (3-B) used for the third flame-retardant laminate is 40 J / g or more, preferably 45 J / g or more, and more preferably 50 J / g or more. If the glass transition temperature of the polyester resin (3-A) is 50 ° C. or more and the heat of crystal fusion ⁇ Hm is 40 J / g or more, there is a problem of insufficient heat resistance during secondary processing and use. Does not occur.
  • the lower limit value of the glass transition temperature of the polyester resin (3-B) used in the third flame retardant laminate and the upper limit value of the heat of crystal fusion ⁇ Hm are not particularly limited, but the glass transition temperature is not limited. Is 100 ° C. or less, and the crystal melting heat ⁇ Hm is 90 J / g or less, a laminate having sufficient heat resistance can be obtained.
  • Examples of the polyvalent carboxylic acid component used in the aliphatic or aromatic polyester obtained by polymerizing the polyvalent carboxylic acid and the polyhydric alcohol include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5- Dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis Aromatic dicarboxylic such as (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid Acid, succinic acid, adipic acid,
  • polyhydric alcohol component examples include diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans-tetramethyl-1, 3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples include 4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), and the like. It is done.
  • These polyhydric alcohol components can be used individually by 1
  • polyester resin composed of the polyvalent carboxylic acid component and the polyhydric alcohol component include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, Examples thereof include polyethylene terephthalate and isophthalate. Among these, it is particularly preferable to use polyethylene terephthalate or polybutylene terephthalate from the viewpoint of heat resistance.
  • the weight average molecular weight of the polyester resin (3-B) obtained by polymerizing the polyvalent carboxylic acid and the polyhydric alcohol is usually 30,000 or more, preferably 35,000 or more, more preferably 40,000 or more. In general, it is 80,000 or less, preferably 75,000 or less, and more preferably 70,000 or less.
  • the weight average molecular weight is 30,000 or more, an appropriate resin cohesive force can be obtained, and the laminate can be prevented from being insufficiently stretched or embrittled.
  • the weight average molecular weight is 80,000 or less, the melt viscosity can be lowered, which is preferable from the viewpoint of production and productivity improvement.
  • Examples of the lactic acid resin used in the third flame-retardant laminate include poly (L-lactic acid) whose structural unit is L-lactic acid, poly (D-lactic acid) whose structural unit is D-lactic acid, Poly (DL-lactic acid), which is D-lactic acid, or a mixture thereof, and further a copolymer with ⁇ -hydroxycarboxylic acid or diol / dicarboxylic acid.
  • the ratio of D-lactic acid is 0.1% or more and less than 3.0%, and more preferably 0.5% or more and less than 2.0%. If it is below this range, the productivity is poor, and if it exceeds this range, the heat resistance of the injection-molded product is difficult to obtain, and the application may be limited.
  • Typical examples of the lactic acid-based resin include “Lacia” series manufactured by Mitsui Chemicals, “Nature Works” series manufactured by Nature Works, and the like.
  • Any known method such as a condensation polymerization method or a ring-opening polymerization method can be employed as a polymerization method of the lactic acid resin.
  • a condensation polymerization method L-lactic acid, D-lactic acid, or a mixture thereof can be directly dehydrated and condensation polymerized to obtain a lactic acid resin having an arbitrary composition.
  • a polylactic acid-based polymer can be obtained using a selected catalyst while using lactide, which is a cyclic dimer of lactic acid, with a polymerization regulator as necessary.
  • Lactide includes L-lactide, which is a dimer of L-lactic acid, D-lactide, which is a dimer of D-lactic acid, and DL-lactide consisting of L-lactic acid and D-lactic acid.
  • a lactic acid resin having an arbitrary composition and crystallinity can be obtained by mixing and polymerizing.
  • the amount of terephthalic acid as a small amount copolymerization component is within a range where the essential properties of the lactic acid resin are not impaired, that is, within a range containing 90% by mass or more of the lactic acid resin component.
  • Non-aliphatic diols such as non-aliphatic dicarboxylic acids and / or ethylene oxide adducts of bisphenol A may be used.
  • a small amount of a chain extender such as a diisocyanate compound, an epoxy compound, and an acid anhydride can be used.
  • the other hydroxycarboxylic acid units copolymerized with the lactic acid resin include optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycolic acid Bifunctional such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyn-butyric acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid, etc.
  • Examples include lactones such as aliphatic hydroxy-carboxylic acid, caprolactone, butyrolactone, and valerolactone.
  • Examples of the aliphatic diol copolymerized with the lactic acid-based resin include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like.
  • Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid.
  • the preferred range of the weight average molecular weight of the lactic acid-based resin is 50,000 to 400,000, preferably 100,000 to 250,000. When the range is below this range, practical properties are hardly expressed. Is inferior in moldability because the melt viscosity is too high.
  • the ratio of the layer thickness of the A layer to the total thickness of the third flame retardant laminate is usually 20% or more, preferably 25% or more, more preferably 30% or more, and usually 95% or less, preferably 85. % Or less, more preferably 70% or less.
  • the ratio of the layer thickness of the A layer is usually 20% or more, preferably 25% or more, more preferably 30% or more, and usually 95% or less, preferably 85. % Or less, more preferably 70% or less.
  • carbodiimide compound In order to further impart hydrolysis resistance to the third flame retardant laminate, a carbodiimide compound can be blended. However, it is not necessary to mix.
  • blend is the same as the carbodiimide compound to mix
  • the amount of the carbodiimide compound is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyester resin (3-A) and / or the polyester resin (3-B). It is more preferable to add 1 to 5 parts by mass. If it is below this range, the effect of imparting durability is low, and if it exceeds this range, the resin composition will be softened and heat resistance may be impaired.
  • additives, resin compositions, cross-linking agents and the like may be contained within a range in which the effect of the third flame retardant laminate is not inhibited.
  • inorganic particles such as silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, and metal fine powder are added. It is preferable because scratch resistance and the like are improved.
  • the average particle diameter of the inorganic particles is preferably 0.005 to 5 ⁇ m, more preferably about 0.05 to 1 ⁇ m.
  • the addition amount is preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight with respect to each of the polyester film, the resin layer, and the primer layer. If the amount added is too large, moldability may be reduced.
  • the peel strength between the A layer and the B layer of the third flame retardant laminate is usually 3 N / cm or more at 23 ° C., preferably 4 N / cm or more, more preferably 5 N / cm or more. If the A layer and the B layer are 3 N / cm or more, the laminate can be used for various purposes as a unit.
  • the tensile strength of the third flame retardant laminate is usually 80 MPa or more, preferably 100 MPa or more, more preferably 120 MPa or more.
  • the tensile strength of the flame retardant laminate is 80 MPa or more, there is no deterioration in workability during secondary processing, breakage of the laminate during use, and the like.
  • the tensile elongation of the third flame retardant laminate is usually 80% or more, preferably 100% or more, more preferably 120% or more. If the tensile elongation of the flame retardant laminate is 80% or more, the laminate will not break during use.
  • lamination can be performed by coextrusion, extrusion lamination, thermal lamination, dry lamination, or the like.
  • a resin composition is prepared by mixing and kneading the raw materials constituting the A layer, and the resin composition a is extruded by a single screw or twin screw extruder, but an extruder different from this.
  • the third flame-retardant laminate can be formed by merging.
  • the laminated film obtained in the above step may be stretched uniaxially or biaxially using a roll method, a tenter method, a tubular method, or the like.
  • the raw material constituting the B layer is mixed and kneaded to prepare a resin composition b, and after extrusion from a T die, I die, etc. using a single screw or twin screw extruder, a roll A film to be the B layer is obtained using a method, a tenter method, a tubular method, or the like.
  • the raw material constituting the A layer is mixed and kneaded to prepare a resin composition a, and the resin composition a is extruded by a single screw or twin screw extruder, simultaneously with the casting of the film to be the A layer.
  • a third flame retardant laminate can be formed by laminating the film to be the B layer. The stretching of the third flame retardant laminate is the same as in the case of coextrusion.
  • the raw material constituting the A layer is mixed and kneaded to prepare the resin composition a, and the resin composition a is T-die, I-die, etc. with a single screw or twin screw extruder
  • the resin composition b is prepared by mixing and kneading the raw materials constituting the B layer, and the resin composition b is formed into a T-die by a single screw or twin screw extruder. Extrude from an I die or the like to obtain a film to be a B layer. Next, the film to be the A layer and the film to be the B layer are heated, or an adhesive layer is disposed between the layers, and the third flame-retardant laminate can be formed by laminating them. it can. The stretching of the third flame retardant laminate is the same as in the case of coextrusion.
  • the surface of the B layer on the A layer side may be subjected to a corona discharge treatment, or an anchor coat layer may be provided on the B layer.
  • the anchor coat adhesive used for the anchor coat layer include polyester, polyurethane, acrylic, and PVC-vinyl acetate copolymer systems.
  • a roll coat method, a gravure coat method, etc. can be used for application
  • the thickness of the anchor coat layer can be appropriately adjusted, but is preferably in the range of 0.1 ⁇ m to 5 ⁇ m from the viewpoint of flame retardancy and adhesiveness.
  • the third flame-retardant laminate has excellent flame retardancy, mechanical properties, and surface properties, an electrical insulating material, a membrane switch circuit printing base material, a copier internal member, a planar heating element base material, It can be used for applications such as FPC reinforcing plates.
  • the present invention provides a new metal-bonding flame-retardant resin laminate having both metal adhesion and flame retardancy without containing a halogen compound and a phosphorus compound. It is to be provided.
  • the present invention is a flame retardant resin laminate for metal adhesion that has both metal adhesion and flame retardancy as a fourth flame retardant laminate, and has a glass transition temperature of ⁇ 80 to 30 ° C. It has an A layer composed of a resin composition a composed mainly of a mixture of polyester resin (4-A), melamine and phenoxy resin, and has a glass transition temperature of 50 to 120 ° C. on the A layer.
  • the body is proposed.
  • the specific polyester resin constituting the adhesive layer (A layer) mainly improves the adhesion between melamine for improving flame retardancy and mainly metal.
  • the flame retardancy can be increased, and the adhesiveness between the adhesive layer (A layer) and the metal can be significantly increased.
  • Phenoxy resin since it does not contain a halogen compound and a phosphorus compound, it is possible to provide a material with excellent safety that does not cause problems such as environmental pollution.
  • Phenoxy resin not only has excellent adhesion to metal because it forms hydrogen bonds with moisture present on the metal surface, but also has compatibility with polyester resin, so phenoxy resin is blended with polyester resin (4-A).
  • the fourth flame retardant laminate has a polyester resin (4-B) formed on a layer A composed of a resin composition a whose main component is a mixture of polyester resin (4-A), melamine and phenoxy resin. It is a laminated body provided with the B layer which consists of the resin composition b which has as a main component.
  • “on the A layer” means not only the case where the B layer is laminated directly on the A layer, but also the case where the B layer is laminated on the A layer via another layer.
  • the A layer is a layer having a role of an adhesive layer, and this A layer is mainly composed of a mixture of the polyester resin (4-A), melamine and phenoxy resin. It is a layer made of the resin composition a.
  • polyester resin (4-A) is a resin having a glass transition temperature of ⁇ 80 ° C. to 30 ° C. If the glass transition temperature of the polyester resin (4-A) is ⁇ 80 ° C. to 30 ° C., a laminate having excellent mechanical properties can be obtained in a wide range from a low temperature to a normal use temperature. From this point of view, the glass transition temperature of the polyester resin (4-A) is particularly preferably ⁇ 70 ° C. or higher, and more preferably ⁇ 60 ° C. or higher. Moreover, it is especially preferable that it is 20 degrees C or less, and it is still more preferable that it is 10 degrees C or less especially.
  • the polyester resin (4-A) is preferably a resin having a heat of crystal fusion ⁇ Hm of 5 to 30 J / g.
  • the heat of crystal melting ⁇ Hm of the polyester resin (4-A) is 5 to 30 J / g, a laminate having sufficient adhesiveness and heat resistance at the time of molding, secondary processing and use, can do.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (4-A) is particularly preferably 8 J / g or more, and more preferably 10 J / g or more. In particular, it is preferably 25 J / g or less, more preferably 20 J / g or less.
  • polyester resin (4-A) one or two or more mixed resins of aliphatic polyester, aromatic aliphatic polyester, and polyester hot melt adhesive can be used. That is, the polyester resin (4-A) may be a single resin or a mixture of two or more resins.
  • polyester resin (4-A) examples include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
  • One or more aliphatic dicarboxylic acids and diethylene glycol ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans-tetramethyl- 1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethyl
  • a copolymer of succinic acid and 1,4-butanediol (“GSPla” AZ series manufactured by Mitsubishi Chemical Corporation, "Bionore” # 1000 series manufactured by Showa Polymer Co., Ltd.), succinic acid, 1,4- Examples include aliphatic polyesters such as polybutylene succinate and adipate copolymers (“GSPla” AD series manufactured by Mitsubishi Chemical Corporation, “Bionore” # 3000 series manufactured by Showa Polymer Co., Ltd.), which are copolymers of butanediol and adipic acid. be able to.
  • the aromatic aliphatic polyester used as the polyester resin (4-A) includes terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid Acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4- One or more aromatic dicarboxylic acids of diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid and ethylene-bis-p-benzoic acid; One or more aliphatic dicarboxylic acids of succinic acid, adipic acid, sebacic acid,
  • a polybutylene adipate-terephthalate copolymer obtained by polymerizing adipic acid, 1,4-butanediol, and terephthalic acid (“Ecoflex” series manufactured by BASF, “manufactured by Eastman Chemicals” And aromatic aliphatic polyesters such as “Easter Bio” series).
  • a copolyester containing at least one polyhydric alcohol component selected from glycol is preferred as the polyester resin (4-A).
  • these aliphatic polyesters and aromatic aliphatic polyesters preferably have a mass average molecular weight of 50,000 to 400,000. If the mass average molecular weight of these polyesters is 50,000 or more, there is no problem that the laminate is damaged due to insufficient flame retardancy or insufficient mechanical strength. Moreover, if a mass average molecular weight is 400,000 or less, the problem of the shaping
  • the mass average molecular weight can be measured by the following method. The same applies to other resins. Using gel permeation chromatography, measurement is made at a solvent chloroform, a solution concentration of 0.2 wt / vol%, a solution injection amount of 200 ⁇ L, a solvent flow rate of 1.0 ml / min, a solvent temperature of 40 ° C., and a mass average molecular weight in terms of polystyrene is obtained. Can be calculated.
  • the mass average molecular weight of the standard polystyrene used in this case is 20000, 430000, 110000, 35000, 10000, 4000, 600.
  • polyester hot melt resin used as the polyester resin (4-A) examples include a resin composition containing as a main component a polyester hot melt resin that is a polycondensation polymer of dibasic acid and glycol.
  • dibasic acids used as raw material monomers for polyester hot melt adhesives include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc.
  • glycols examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol.
  • a hot melt resin made of a polyester resin containing adipic acid, 1,4-butanediol or the like in the molecular skeleton is preferably used.
  • polyester hot melt resins include “Nichigo Polyester” series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. and “Byron” series manufactured by Toyobo Co., Ltd.
  • the mass average molecular weight of the polyester hot melt adhesive is preferably 20,000 to 120,000. If it is this range, since it has a mechanical characteristic sufficient practically and melt viscosity is suitable, possibility that a problem will generate
  • melamine Melamine is similar to the melamine used in the first flame retardant resin composition, and can obtain the same action. Similarly to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination as long as the effects of the fourth flame retardant laminate are not impaired. Melamine generates a non-flammable gas during combustion, so that not only the A layer can be made flame retardant, but also the B layer can be made flame retardant, making it difficult for the entire fourth flame retardant laminate. The flammability can be greatly increased.
  • the phenoxy resin is the same as the phenoxy resin used in the second flame retardant resin composition, and the same action can be obtained.
  • the blending ratio of melamine in the resin composition a constituting the A layer is 20 to 80% by mass. If the blending ratio of melamine in the resin composition a constituting the A layer is 20% by mass or more, sufficient flame retardancy can be obtained. On the other hand, if the blending ratio of melamine is 80% by mass or less, the mechanical properties of the fourth flame retardant laminate will not be impaired. From this viewpoint, the blending ratio of melamine in the resin composition a constituting the A layer is preferably 30% by mass or more, and more preferably 40% by mass or more. Moreover, it is preferable that it is 70 mass% or less, and it is still more preferable that it is 60 mass% or less especially.
  • the proportion of the phenoxy resin in the resin composition a constituting the A layer is 1 to 30% by mass. If it falls below this range, the effect of improving adhesion to metal is hardly obtained, and if it exceeds this range, mechanical properties, particularly impact resistance, may be reduced. From this viewpoint, the ratio of the phenoxy resin in the resin composition a constituting the A layer is preferably 5% by mass or more, and preferably 20% by mass or less.
  • the B layer is a layer made of the resin composition b mainly composed of a polyester resin (4-B).
  • polyester resin (4-B) As the polyester resin (4-B), it is important to use a polyester resin having a glass transition temperature of 50 to 120 ° C. and a crystal melting heat ⁇ Hm of 40 to 100 J / g. By satisfying this condition, a laminate having excellent heat resistance can be provided.
  • the glass transition temperature of the polyester resin (4-B) is 50 to 120 ° C. as described above.
  • the glass transition temperature of the polyester resin (4-B) is 50 to 120 ° C., a laminate having excellent molding processability and excellent heat resistance during use can be obtained.
  • the glass transition temperature of the polyester resin (4-B) is preferably 55 ° C. or higher, and more preferably 60 ° C. or higher.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (4-B) is 40 to 100 J / g as described above.
  • the heat of crystal melting ⁇ Hm of the polyester resin (4-B) is 40 to 100 J / g, problems such as deformation during secondary processing do not occur.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (4-B) is preferably 45 J / g or more, and more preferably 50 J / g or more. Further, it is preferably 90 J / g or less, more preferably 80 J / g or less.
  • polyester resin (4-B) examples include aromatic polyesters obtained by polymerizing polyvalent carboxylic acids and polyhydric alcohols, and aliphatic polyesters such as lactic acid resins.
  • examples of the polyvalent carboxylic acid component used in the aliphatic polyester or aromatic polyester include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4, 4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, succinic acid, adipic acid, sebacic acid, azelain Acid, dode
  • polyhydric alcohol component examples include diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and trans-tetramethyl-1,3.
  • polyester resin composed of the polyvalent carboxylic acid component and the polyhydric alcohol component include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, Examples thereof include polyethylene terephthalate and isophthalate. Among these, it is particularly preferable to use polyethylene terephthalate or polybutylene terephthalate from the viewpoint of heat resistance.
  • the mass average molecular weight of the polyester resin (4-B) is preferably 30,000 to 80,000. If the mass average molecular weight of the polyester-based resin (4-B) is 30,000 or more, an appropriate resin cohesive force can be obtained, and the strength and elongation of the laminate can be prevented from being insufficient or brittle. it can. On the other hand, if it is 80,000 or less, the melt viscosity can be lowered, which is preferable from the viewpoint of production and productivity improvement. From this viewpoint, the mass average molecular weight of the polyester resin (4-B) is particularly preferably 35,000 or more, and more preferably 40,000 or more. Further, it is particularly preferably 75,000 or less, and more preferably 70,000 or less.
  • the B layer may be composed of a stretched film, and in that case, it is preferably composed of a biaxially stretched film.
  • a carbodiimide compound may be blended in the resin composition a constituting the A layer and the resin composition b constituting the B layer in order to impart hydrolysis resistance. However, it is not necessary to mix.
  • the kind of the carbodiimide compound to be blended is the same as the carbodiimide compound to be blended explained in the first flame retardant resin composition.
  • the amount of the carbodiimide compound is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyester resin (4-A) or 100 parts by mass of the polyester resin (4-B). It is more preferable to blend 5 parts by mass. If it is below this range, the effect of imparting durability is low, and if it exceeds this range, the resin composition will be softened and heat resistance may be impaired.
  • the ratio of the layer thickness of the A layer to the total thickness of the fourth flame retardant laminate is preferably 20 to 70%.
  • the ratio of the layer thickness of the A layer is particularly preferably 25% or more, and more preferably 30% or more. Further, it is particularly preferably 60% or less, and more preferably 50% or less.
  • the 4th flame-retardant laminated body may be provided with layers other than A layer and B layer.
  • another layer may be interposed between the A layer and the B layer, or another layer may be provided outside the B layer (on the opposite side to the A layer).
  • the thickness of the fourth flame-retardant laminate is not particularly limited, and can be adjusted to a thickness suitable for each application, such as a film, a sheet, or a panel.
  • the peel strength between the A layer and the B layer is preferably 3 N / cm or more at 23 ° C., more preferably 4 N / cm or more, and particularly preferably 5 N / cm or more.
  • the peel strength between the A layer and the metal is 23 ° C. 5 N / cm or more, particularly preferably 6 N / cm or more, and particularly preferably 7 N / cm or more.
  • the peel strength between the A layer and the B layer is 3 N / cm or more and the peel strength between the A layer and the metal conductor (particularly tin-plated copper foil) is 5 N / cm or more, various uses as a laminate are possible. This is even more preferable.
  • the fourth flame retardant laminate can be produced in the same manner as the third flame retardant laminate described above.
  • the fourth flame retardant laminate can not only achieve flame retardancy, particularly flame retardancy satisfying the V94-0 standard of UL94 vertical combustion test UL94VTM, but also adhere to metal, especially copper. Since excellent metal adhesiveness can be obtained, for example, it can be suitably used as a coating resin film for coating a metal conductor. That is, a wiring cable can be produced by using two fourth flame retardant laminates, placing metal conductors between these A layers, and bonding the four fourth flame retardant laminates together. . In particular, the fourth flame retardant laminate can obtain not only excellent flame retardancy and metal adhesion as described above, but also excellent flexibility and excellent heat resistance. Especially suitable for flat cables.
  • the fourth flame retardant laminate is excellent in adhesiveness with metals other than copper, such as silver, gold, platinum, iron, stainless steel, steel or alloys thereof.
  • metals other than copper such as silver, gold, platinum, iron, stainless steel, steel or alloys thereof.
  • it can be suitably used for other applications where flame retardancy and metal adhesion are required.
  • a reinforcement board and a label are mentioned.
  • the reinforcing plate refers to a plate attached to the end of the wiring cable.
  • the fifth flame-retardant laminate provides a laminate having excellent flame retardancy and excellent heat resistance and mechanical properties without containing a halogen-based compound and a phosphorus-based compound. . That is, the fifth flame retardant laminate has a glass transition temperature on at least one side of the A layer mainly composed of a mixture of a polyester resin (5-A) having a glass transition temperature of 20 ° C. or lower, melamine and a crosslinking agent.
  • the heat-resistant flame-retardant laminate is characterized in that the proportion of melamine occupied is 10% by mass or more and 40% by mass or less.
  • polyester resin (5-A) It is important that the polyester resin (5-A) has a glass transition temperature of 20 ° C. or lower. By satisfying this condition, the adhesiveness with the B layer made of the polyester resin (5-B) having a glass transition temperature of 60 ° C. or higher is good, and the secondary processing and peeling between the layers at the time of use are performed. It is possible not only to provide a laminate that does not cause the occurrence of the problem, but also to provide a laminate having excellent mechanical strength.
  • the polyester resin (5-A) may be a single resin or a mixture of two or more resins.
  • the glass transition temperature of the polyester resin (5-A) used for the fifth flame-retardant laminate is 20 ° C. or lower, preferably 10 ° C. or lower, and more preferably 0 ° C. or lower. If the glass transition temperature of the polyester-based resin (5-A) is 20 ° C. or lower, the problem of peeling from the B layer made of the polyester-based resin (5-B) during molding, secondary processing, and use Not only does not occur, but also excellent mechanical properties (particularly tensile elongation) can be imparted to the flame retardant laminate.
  • the lower limit of the glass transition temperature of the polyester resin (5-A) is not particularly limited, but the polyester resin can be used in all practical temperature ranges as long as the glass transition temperature is ⁇ 100 ° C.
  • polyester resin As the polyester resin (5-A), aliphatic polyesters, aromatic aliphatic polyesters, or polyester hot melt adhesives having a glass transition temperature of 20 ° C. or less are used alone or in combination. Can be used by.
  • Examples of the aliphatic polyester include polybutylene succinate obtained by polymerizing succinic acid and 1,4-butanediol (“GSPla” AZ series manufactured by Mitsubishi Chemical Corporation, “Bionore” # 1000 series manufactured by Showa Polymer Co., Ltd., etc.) Is mentioned.
  • Examples of the aliphatic polyester include polybutylene succinate-adipate copolymers obtained by polymerizing succinic acid, 1,4-butanediol, and adipic acid (“GSPla” AD series manufactured by Mitsubishi Chemical Corporation, Showa Polymer Co., Ltd.) “Bionore” # 3000 series manufactured by the company and the like can be mentioned.
  • aromatic aliphatic polyester examples include polybutylene adipate-terephthalate copolymers obtained by polymerizing adipic acid, 1,4-butanediol, and terephthalic acid ("Ecoflex” series manufactured by BASF, Eastman Chemicals) "Easter Star” series).
  • the lower limit of the weight average molecular weight of the aliphatic polyester and the aromatic aliphatic polyester is 50,000 or more, preferably 80,000 or more, more preferably 100,000 or more.
  • the weight average of the aromatic aliphatic polyester The upper limit of the molecular weight is 400,000 or less, preferably 300,000 or less, more preferably 250,000 or less.
  • the weight average molecular weight of the aromatic aliphatic polyester is 50,000 or more, the mechanical properties during use are not deteriorated, and the weight average molecular weight of the aromatic aliphatic polyester is 400,000 or less. Therefore, the viscosity at the time of processing becomes optimum, and the problem of poor thickness of the laminate or poor dispersion of melamine does not occur.
  • the weight average molecular weight is a value measured by the following method. That is, using gel permeation chromatography, using chloroform as a solvent (solution concentration 0.2 wt / vol%, solution injection amount 200 ⁇ l, solvent flow rate 1.0 ml / min, solvent temperature 40 ° C.)
  • the weight average molecular weight of the polyester resin can be calculated in terms of polystyrene.
  • the weight average molecular weight of the standard polystyrene used is 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, 600.
  • polyester hot melt adhesive a resin composition containing as a main component a polyester hot melt resin that is a polycondensation polymer of dibasic acid and glycol (Toyobo Co., Ltd. “Byron” (registered trademark) series, Nippon Synthetic Chemical Industry “Nichigo Polyester” series) and the like.
  • dibasic acids used as raw material monomers for polyester hot melt adhesives include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc.
  • glycols examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol.
  • a hot melt resin made of a polyester resin containing adipic acid, 1,4-butanediol, or the like in the molecular skeleton is preferably used.
  • the lower limit of the weight average molecular weight of the polyester hot melt adhesive is 20,000 or more, preferably 25,000 or more, more preferably 30,000 or more, and the upper limit of the number average molecular weight is 120,000 or less, Preferably it is 110,000 or less, More preferably, it is 100,000 or less. If the weight average molecular weight of the polyester-based hot melt adhesive is in the range of 20,000 or more and 120,000 or less, there is a problem in the molding process because it has practically sufficient mechanical properties and an appropriate melt viscosity. Is less likely to do.
  • melamine Melamine is similar to the melamine used in the first flame retardant resin composition, and can obtain the same action. Similarly to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination as long as the effects of the fifth flame retardant laminate are not impaired.
  • the content of melamine in the entire fifth flame-retardant laminate is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and 40% by mass or less, preferably 35% by mass or less. More preferably, it is more preferably 30% by mass or less.
  • the content of melamine in the resin composition constituting the fifth flame retardant laminate is 10% by mass or more, sufficient flame retardancy can be imparted.
  • the content of melamine is 40% by mass or less, the mechanical properties of the layer having no flame retardancy are not significantly lowered, and the mechanical properties of the entire laminate are not impaired.
  • the surface-treated melamine and non-surface-treated melamine may be mixed or used only with surface-treated melamine. May be.
  • the content of the surface-treated melamine is 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass with respect to the mass of all melamine components of the fifth flame retardant laminate.
  • the upper limit is 100% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less.
  • excellent dispersibility can be imparted by the surface treatment, and when the content is 100% by mass or less, problems such as reduction in mechanical properties and increase in viscosity do not occur.
  • Cross-linking agent As the cross-linking agent used in the fifth flame retardant laminate, a compound having a molecular weight of about 2000 or less and having two or more functional groups such as acryl group, methacryl group, allyl group and vinyl group in the molecule can be suitably used. .
  • diallyl isocyanate diallyl isocyanate, triallyl isocyanate, dimethallyl isocyanate, trimethallyl isocyanate, diallyl monoglycidyl isocyanate, 1,4-butanediol dimethacrylate, polyethylene glycol methacrylate, pentaerythritol dimethacrylate, dipenta Examples include erythritol hexaacrylate, trimethylolpropane acrylate, divinylbenzene, trivinylbenzene, and hexamethylbenzene.
  • the ratio of the crosslinking agent to A layer is 0.1 to 5 mass%, and it is 0.5 to 4 mass%. More preferably, the content is 1% by mass or more and 3% by mass or less.
  • polyester resin (5-B) As the polyester resin (5-B), it is important that the glass transition temperature is 60 ° C. or higher. By satisfying this condition, a laminate having excellent heat resistance can be provided.
  • Specific examples of the polyester resin (5-B) include aliphatic polyesters such as aromatic polyesters and lactic acid resins obtained by polymerizing polyvalent carboxylic acids and polyhydric alcohols.
  • the lower limit value of the glass transition temperature of the polyester resin (5-B) is 60 ° C. or higher, preferably 65 ° C. or higher, and more preferably 70 ° C. or higher. If the lower limit of the glass transition temperature of the polyester resin (5-B) is 60 ° C. or higher, there will be no problem of insufficient heat resistance during secondary processing and use.
  • the lower limit of the glass transition temperature of the polyester-based resin (5-B) is not particularly limited. However, if the glass transition temperature is 100 ° C. or less, sufficient flame retardancy, heat resistance, mechanical properties are obtained. Is obtained.
  • the lower limit value of the heat of crystal fusion ⁇ Hm of the polyester resin (5-B) is 45 J / g or more, preferably 50 J / g or more, more preferably 55 J / g or more, the heat resistance is further improved.
  • a laminate can be provided.
  • examples of the polyvalent carboxylic acid component used in the aliphatic and aromatic polyester obtained by polymerizing the polyvalent carboxylic acid and the polyhydric alcohol include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2 , 5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid Acids, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, etc.
  • Aromatic dicarboxylic acid succinic acid, adipic acid, sebacic acid, azerai Acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acid component and 1,4-cyclohexane dicarboxylic acid.
  • These polyvalent carboxylic acid components can be used alone or in combination of two or more.
  • polyhydric alcohol component examples include diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans-tetramethyl-1, 3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples include 4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), and the like. It is done.
  • These polyhydric alcohol components can be used alone or in
  • polyester resin composed of the polyvalent carboxylic acid component and the polyhydric alcohol component include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, Examples include polyethylene terephthalate / isophthalate and polytrimethylene terephthalate. Among these, it is particularly preferable to use polyethylene terephthalate or polybutylene terephthalate from the viewpoint of heat resistance.
  • the weight average molecular weight of the polyester resin (5-B) obtained by polymerizing the polyvalent carboxylic acid and the polyhydric alcohol is usually 30,000 or more, preferably 35,000 or more, more preferably 40,000 or more. In general, it is 80,000 or less, preferably 75,000 or less, and more preferably 70,000 or less.
  • the weight average molecular weight is 30,000 or more, an appropriate resin cohesive force can be obtained, and the laminate can be prevented from being insufficiently stretched or embrittled.
  • the weight average molecular weight is 80,000 or less, the melt viscosity can be lowered, which is preferable from the viewpoint of production and productivity improvement.
  • the ratio of the thickness of layer A to the total thickness of the fifth flame-retardant laminate is such that the proportion of melamine in the resin composition constituting the entire laminate is 10% by mass or more and 40% by mass or less.
  • the layer thickness is usually 20% or more, preferably 25% or more, more preferably 30% or more, 70% or less, preferably 60% or less, more preferably 50%. It is as follows. By setting the ratio of the layer thickness of the A layer to 20% or more and 70% or less, sufficient flame retardancy, heat resistance, and mechanical properties can be imparted to the flame retardant laminate.
  • a carbodiimide compound In order to further impart hydrolysis resistance to the fifth flame retardant laminate, a carbodiimide compound can be blended. However, it is not necessary to mix.
  • blend is the same as the carbodiimide compound to mix
  • the blending amount of the carbodiimide compound is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyester resin (5-A) and / or the polyester resin (5-B). It is preferable to mix
  • various additives, resin compositions, cross-linking agents and the like may be contained within a range in which the effect of the fifth flame-retardant laminate is not inhibited.
  • inorganic particles such as silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, and metal fine powder are added. It is preferable because scratch resistance and the like are improved.
  • the average particle size of the inorganic particles is preferably 0.005 ⁇ m or more and 5 ⁇ m or less, and more preferably 0.05 ⁇ m or more and 1 ⁇ m or less.
  • the addition amount is 0.05 mass% or more with respect to each of the resin composition which comprises A layer, B layer, or the resin composition which comprises the adhesive layer of A layer and B layer, 20 It is preferable to mix
  • the fifth flame retardant laminate can be produced in the same manner as the third flame retardant laminate described above. However, in the fifth flame-retardant laminate, the A layer and the B layer, the A layer, or the B layer can be stretched.
  • the stretch ratio of the A layer and / or the B layer is 1.5 times in MD (longitudinal direction), preferably 3 times, more preferably 5 times, and 1.5 times in TD (lateral direction). This is 3 times, more preferably 5 times.
  • the stretching can be performed in MD and / or TD, but it is preferable to stretch in MD and TD from the viewpoint of improving heat resistance and mechanical properties.
  • the ionizing radiation include ultraviolet rays / electron beams / ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, etc.
  • the irradiation dose of ionizing radiation is preferably 10 kGy or more and 100 kGy or less, more preferably 20 kGy or more and 80 kGy or less, and further preferably 30 kGy or more and 70 kGy or less.
  • the irradiation time is not particularly limited, and it is sufficient to perform a time for sufficiently completing the crosslinking reaction of the laminate.
  • the gel fraction of the laminate is 15% by mass or more and 55% by mass or less, more preferably 20% by mass or more and 40% by mass or less, and more preferably 25% by mass or more, 45% by mass. More preferably, it is at most mass%.
  • the gel fraction is less than 15% by mass, sufficient heat resistance imparting effect cannot be obtained, and when it exceeds 55% by mass, the appearance and mechanical strength may be impaired due to excessive crosslinking.
  • the fifth flame retardant laminate has excellent flame retardancy, heat resistance, and mechanical properties. Therefore, an electrical insulating material, a membrane switch circuit printing substrate, a copier internal member, a planar heating element substrate, It can be used for applications such as FPC reinforcing plates.
  • the gel fraction of the resin composition which comprises a 5th flame retardant laminated body is a value measured as follows. (1) A test piece of 0.25 g cut from the laminate is dissolved in 20 ml of chloroform at 23 ° C. for 5 hours. (2) The solution prepared in the above (1) is separated into insoluble matters at a rotation speed of 11,400 rpm using a table top high-speed cooling centrifuge 3-18K manufactured by Sigma Laborentrifugen GmbH. (3) After drying the insoluble matter obtained in (2) above and subtracting components other than the resin component (for example, melamine, inorganic matter), the gel fraction is calculated by the following equation.
  • Gel fraction (mass%) A / B ⁇ 100
  • A The mass of the insoluble matter of the resin component after subtracting the mass of the components other than the resin component obtained in (3) (for example, melamine, inorganic).
  • B Theoretical mass of the resin component obtained by subtracting the mass of components other than the resin component in the laminate (for example, melamine, inorganic).
  • the amount of melamine added may be calculated from the intensity of the peak (815 cm-1) derived from the triazine ring of melamine by IR (infrared absorption analysis) measurement.
  • the addition amount of the inorganic material may be calculated from the sum of the inorganic elements by elemental analysis.
  • the sixth flame-retardant laminate has a layer comprising a resin composition a having a glass transition temperature of 30 ° C. or lower as a main component and a mixture of a melamine and a carbonization accelerator.
  • B is composed of a resin composition b composed mainly of a polyester resin (6-B) having a glass transition temperature of 50 to 120 ° C. and a crystal melting heat ⁇ Hm of 40 to 100 J / g.
  • This sixth flame-retardant laminate can express a higher degree of flame retardancy by blending melamine and a carbonization accelerator in a specific polyester resin constituting the adhesive layer (A layer). .
  • a carbonization accelerator since it does not contain a halogen compound and a phosphorus compound, it is possible to provide a material with excellent safety that does not cause problems such as environmental pollution. Since melamine generates nonflammable gas when burned, not only can the adhesive layer be flame retardant, but also the outer layer (B layer) that does not contain a flame retardant can also be flame retardant. The flame retardance of the entire laminate can be significantly increased.
  • carbonization of the resin proceeds rapidly during combustion, and a wiring cable laminate capable of satisfying the UL1581VW-1 standard can be provided.
  • the sixth flame retardant laminate comprises a polyester resin (6-A) on a layer A composed of a resin composition a having a polyester resin (6-A), a mixture of melamine and a carbonization accelerator as main components. It is a laminated body provided with B layer which consists of the resin composition b which has B) as a main component.
  • “on the A layer” includes not only the case where the B layer is laminated directly on the A layer, but also the case where the B layer is laminated on the A layer via another layer. Details will be described below.
  • the A layer is a layer having a role of an adhesive layer, and this A layer is mainly composed of a mixture comprising a polyester resin (6-A), melamine and a carbonization accelerator. It is the layer which consists of the resin composition a to do.
  • the polyester resin (6-A) is a resin having a glass transition temperature of 30 ° C. or lower. If the glass transition temperature of the polyester resin (6-A) is 30 ° C. or lower, a laminate having excellent mechanical properties can be obtained in a wide range from a low temperature to a normal use temperature. From such a viewpoint, the glass transition temperature of the polyester resin (6-A) is preferably ⁇ 80 ° C. or higher, more preferably ⁇ 70 ° C. or higher, and particularly preferably ⁇ 60 ° C. or higher. Moreover, it is preferable that it is 20 degrees C or less, and it is especially preferable that it is 10 degrees C or less.
  • the polyester resin (6-A) is preferably a resin having a heat of crystal fusion ⁇ Hm of 5 to 30 J / g.
  • the heat of crystal melting ⁇ Hm of the polyester resin (6-A) is 5 to 30 J / g, a laminate having sufficient adhesiveness and heat resistance at the time of molding, secondary processing and use, can do.
  • the heat of crystal fusion ⁇ Hm of the polyester-based resin (6-A) is preferably 8 J / g or more, and more preferably 10 J / g or more.
  • polyester resin (6-A) one or a mixture of two or more of aliphatic polyester, aromatic aliphatic polyester, and polyester hot melt adhesive can be used. That is, the polyester resin (6-A) may be a single resin or a mixture of two or more resins.
  • polyester resin (6-A) examples include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
  • One or more aliphatic dicarboxylic acids and diethylene glycol ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans-tetra Methyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexane Diol, 1,4-cyclohexanedimethanol, 1,3-cyclohexane
  • One or two or more polyhydric alcohols selected from methanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis (2-hydroxyethyl ether
  • a copolymer of succinic acid and 1,4-butanediol (“GSPla” AZ series manufactured by Mitsubishi Chemical Corporation, "Bionore” # 1000 series manufactured by Showa Polymer Co., Ltd.), succinic acid, 1,4- Examples include aliphatic polyesters such as polybutylene succinate and adipate copolymers (“GSPla” AD series manufactured by Mitsubishi Chemical Corporation, “Bionore” # 3000 series manufactured by Showa Polymer Co., Ltd.), which are copolymers of butanediol and adipic acid. be able to.
  • polyester resin (6-A) examples include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, and 4,4-stilbene dicarboxylic acid.
  • Acid 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4- One or more of diphenyl ether dicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid and ethylene-bis-p-benzoic acid, and succinic acid, Adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3- One or more aliphatic dicarboxylic acids of chlorohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid and diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2, 2-
  • a polybutylene adipate-terephthalate copolymer obtained by polymerizing adipic acid, 1,4-butanediol, and terephthalic acid (“Ecoflex” series manufactured by BASF, "Easter” manufactured by Eastman Chemicals, Inc. Aromatic aliphatic polyesters such as “Bio” series).
  • a copolyester containing at least one polyhydric alcohol component selected from glycols is preferred as the polyester resin (6-A).
  • These aliphatic polyesters and aromatic aliphatic polyesters preferably have a mass average molecular weight of 50,000 to 400,000. If the mass average molecular weight of these polyesters is 50,000 or more, there is no problem that the laminate is damaged due to insufficient flame retardancy or insufficient mechanical strength. Moreover, if a mass average molecular weight is 400,000 or less, the problem of the shaping
  • the mass average molecular weight can be measured by the following method. The same applies to other resins. Using gel permeation chromatography, measurement was performed at a solvent chloroform, a solution concentration of 0.2 wt / volume%, a solution injection amount of 200 ⁇ L, a solvent flow rate of 1.0 ml / min, a solvent temperature of 40 ° C., and a mass average molecular weight in terms of polystyrene. Can be calculated.
  • the mass average molecular weight of the standard polystyrene used in this case is 20000, 430000, 110000, 35000, 10000, 4000, 600.
  • the polyester hot melt resin used as the polyester resin (6-A) is the same as the polyester hot melt adhesive used for the polyester resin (5-A) of the fifth flame-retardant laminate.
  • melamine Melamine is similar to the melamine used in the first flame retardant resin composition, and can obtain the same action. Similarly to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination as long as the effects of the fifth flame retardant laminate are not impaired.
  • the carbonization accelerator is an inorganic substance or an organic substance that can promote carbonization of the resin at the time of combustion.
  • Specific examples include polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, guanidine sulfamate, Guanidine compounds such as guanidine phosphate, sulfuric acid compounds such as melamine sulfate and ammonium sulfate, nitric acid compounds such as melamine nitrate and ammonium nitrate, phenoxy resins having a hydroxyl group, silicone oil, silicone rubber, silicone compounds such as silicone resin, melamine cyanurate, water Metal hydroxides such as calcium oxide, aluminum hydroxide, magnesium hydroxide, calcium / aluminate hydrate, tin oxide hydrate, talc, mica, zinc borate, zinc oxide, magnesium oxide, etc.
  • the adhesive strength with a metal can also be improved.
  • the said carbonization promoter can be used individually or in mixture of 2 or more types.
  • Examples of the compound having a hydroxyl group used in the sixth flame retardant laminate include metal hydroxide such as aluminum hydroxide, ammonium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide, iron hydroxide and the like. And organic substances such as polyvinyl alcohol, phenoxy resin, urethane resin, cellulose ether, lignin, sucrose, chitosan, pentaerythritol, dipentaerythritol, and tripentaerythritol.
  • metal hydroxide such as aluminum hydroxide, ammonium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide, iron hydroxide and the like.
  • organic substances such as polyvinyl alcohol, phenoxy resin, urethane resin, cellulose ether, lignin, sucrose, chitosan, pentaerythritol, dipentaerythritol, and tripentaeryth
  • the phenoxy resin is the same as the phenoxy resin used in the second flame retardant resin composition, and the same action can be obtained.
  • the blending ratio of melamine in the resin composition a constituting the A layer is 20 to 80% by mass. If the blending ratio of melamine in the resin composition a constituting the A layer is 20% by mass or more, sufficient flame retardancy can be obtained. On the other hand, if the blending ratio of melamine is 80% by mass or less, the mechanical properties of the sixth flame retardant laminate will not be impaired. From this viewpoint, the blending ratio of melamine in the resin composition a constituting the A layer is preferably 30% by mass or more, and more preferably 40% by mass or more. Moreover, it is preferable that it is 70 mass% or less, and it is still more preferable that it is 60 mass% or less especially.
  • the blending ratio of the carbonization accelerator in the resin composition a constituting the A layer is 1 to 30% by mass.
  • the blending ratio of the carbonization accelerator in the resin composition a constituting the A layer is 1% by mass or more, a sufficient carbonization promoting effect can be obtained.
  • the blending ratio of melamine is 30% by mass or less, the mechanical properties of the sixth flame retardant laminate will not be impaired.
  • the blending ratio of melamine in the resin composition a constituting the A layer is preferably 1% by mass or more, and more preferably 5% by mass or more. Moreover, it is preferable that it is 30 mass% or less, and it is still more preferable that it is 20 mass% or less especially.
  • the B layer is a layer made of the resin composition b mainly composed of a polyester resin (6-B).
  • polyester resin (6-B) As the polyester resin (6-B), it is important to use a polyester resin having a glass transition temperature of 50 to 120 ° C. and a crystal melting heat ⁇ Hm of 40 to 100 J / g. By satisfying this condition, a laminate having excellent heat resistance can be provided.
  • the glass transition temperature of the polyester resin (6-B) is 50 to 120 ° C. as described above.
  • the glass transition temperature of the polyester resin (6-B) is 50 to 120 ° C., a laminate having excellent moldability and excellent heat resistance during use can be obtained.
  • the glass transition temperature of the polyester resin (6-B) is preferably 55 ° C. or higher, and more preferably 60 ° C. or higher.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (6-B) is 40 to 100 J / g as described above.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (6-B) is preferably 45 J / g or more, and more preferably 50 J / g or more. Further, it is preferably 90 J / g or less, more preferably 80 J / g or less.
  • polyester resin (6-B) examples include aromatic polyesters obtained by polymerizing polyvalent carboxylic acids and polyhydric alcohols, and aliphatic polyesters such as lactic acid resins.
  • examples of the polyvalent carboxylic acid component used in the aliphatic polyester or aromatic polyester include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4, 4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, succinic acid, adipic acid, sebacic acid, azelain Acid, dode
  • polyhydric alcohol component examples include diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and trans-tetramethyl-1,3.
  • polyester resin composed of the polyvalent carboxylic acid component and the polyhydric alcohol component include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, Examples thereof include polyethylene terephthalate and isophthalate. Among these, it is particularly preferable to use polyethylene terephthalate or polybutylene terephthalate from the viewpoint of heat resistance.
  • the mass average molecular weight of the polyester resin (6-B) is preferably 30,000 to 80,000. If the mass average molecular weight of the polyester-based resin (6-B) is 30,000 or more, an appropriate resin cohesive force can be obtained, and it is possible to prevent the laminate from being insufficient in strength or brittle. it can. On the other hand, if it is 80,000 or less, the melt viscosity can be lowered, which is preferable from the viewpoint of production and productivity improvement. From this viewpoint, the mass average molecular weight of the polyester resin (6-B) is particularly preferably 35,000 or more, and more preferably 40,000 or more. Further, it is particularly preferably 75,000 or less, and more preferably 70,000 or less.
  • the B layer may be composed of a stretched film, and in that case, it is preferably composed of a biaxially stretched film.
  • a carbodiimide compound may be blended with the resin composition a constituting the A layer and the resin composition b constituting the B layer in order to impart hydrolysis resistance. However, it is not necessary to mix.
  • the kind of the carbodiimide compound to be blended is the same as the carbodiimide compound to be blended explained in the first flame retardant resin composition.
  • the amount of the carbodiimide compound is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the polyester resin (6-A) or 100 parts by mass of the polyester resin (6-B). It is more preferable to add 1 to 5 parts by mass. If it is below this range, the effect of imparting durability is low, and if it exceeds this range, the resin composition will be softened and heat resistance may be impaired.
  • an additive for imparting a function is added within a range not inhibiting the effect of the sixth flame retardant laminate.
  • the additive for imparting a function include a conductive agent, a smoke preventive agent, a plasticizer, a lubricant, an antioxidant, an ultraviolet absorber, a pigment, and other fillers.
  • different resins include polyolefin resins, styrene resins, polyolefin resins, acrylic resins, polycarbonate resins, polyamide resins, and the like.
  • the ratio of the layer thickness of the A layer to the total thickness of the sixth flame retardant laminate is preferably 20 to 70%.
  • the ratio of the layer thickness of the A layer is particularly preferably 25% or more, and more preferably 30% or more. Further, it is particularly preferably 60% or less, and more preferably 50% or less.
  • the A layer thickness is usually 10 ⁇ m or more, preferably 20 ⁇ m or more, more preferably 40 ⁇ m or more, and usually 200 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the B layer thickness is usually 10 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and is usually 200 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the sixth flame retardant laminate may include a layer other than the A layer and the B layer.
  • another layer may be interposed between the A layer and the B layer, or another layer may be provided outside the B layer (on the opposite side to the A layer).
  • the thickness of the sixth flame-retardant laminate is not particularly limited, and can be adjusted to a thickness suitable for each application such as a film, a sheet, and a panel.
  • the sixth flame-retardant laminate has very excellent flame retardancy, and can satisfy UL1581VW-1, which is one index for evaluating the flame retardancy. That is, the sixth flame retardant laminate comprises a polyester resin (A) satisfying a certain condition, a layer A composed mainly of melamine and a carbonization accelerator, and a polyester resin (6- By configuring the B layer with B) as a main component, it is possible to satisfy UL1581VW-1.
  • the sixth flame retardant laminate can be produced in the same manner as the third flame retardant laminate described above.
  • the sixth flame-retardant laminate can obtain flame retardancy, particularly flame retardancy satisfying the UL1581VW-1 standard, and can be suitably used, for example, as a covering resin film for covering a wiring cable. That is, a wiring cable can be produced by using two sixth flame retardant laminates, placing metal conductors between these A layers, and bonding the two laminates together.
  • the sixth flame-retardant laminate can obtain not only excellent flame retardancy but also excellent flexibility and excellent heat resistance as described above. Particularly suitable as.
  • the expression “main component” includes the meaning of allowing other components to be contained within a range that does not hinder the function of the main component unless otherwise specified.
  • the content ratio of the main component is not particularly specified, its component (when two or more components are main components, the total amount thereof) is 60% by mass or more, particularly 70% by mass or more in the composition. Of these, 90% by mass or more (including 100%) is preferable.
  • the mixture in the resin composition a preferably occupies 60% by mass or more, particularly 70% by mass or more, particularly 90% by mass or more (including 100%) in the resin composition a.
  • X to Y (X and Y are arbitrary numbers) is described, it means “X or more and Y or less” unless otherwise specified. The meaning of “preferably smaller than Y” is included. In addition, when “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
  • film refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, usually supplied in the form of a roll.
  • sheet generally refers to a product that is thin by definition in JIS and whose thickness is small and flat instead of length and width.
  • sheet since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
  • the “wiring cable” means a structure having a structure in which a metal conductor is covered with a resin film.
  • a flat having a structure in which two or more metal conductors are arranged and covered with a resin film.
  • a cable is a typical example.
  • the “glass transition temperature” and “crystal heat of fusion” of the polyester resin in the present invention are values measured as follows. In Examples and Comparative Examples described later, the measurement was performed by the method described below unless otherwise specified.
  • a polyester-based resin is formed into a scale of about 10 mg having a diameter of 5 mm and used as a test sample.
  • the test sample obtained in (1) above was held at 200 ° C. for 2 minutes based on JIS-K7121 using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer), and then 10 ° C./min The temperature is decreased to ⁇ 40 ° C. Next, the temperature rise is measured from ⁇ 40 ° C. to 200 ° C. at 10 ° C./min. A series of measurements are performed in a nitrogen atmosphere.
  • the glass transition temperature and the heat of crystal melting are read from the thermogram obtained by the measurement of (2).
  • samples with a thickness of 200 ⁇ m or less are judged on the basis of the UL94VTM criteria whether or not the VTM-0, 1 and 2 standards are satisfied.
  • a product satisfying VTM-0 was evaluated as an acceptable product.
  • samples with a thickness exceeding 200 ⁇ m whether or not the standards of VTM-0, 1 and 2 are satisfied is judged based on the UL94V criteria, and those not satisfying VTM-2 are evaluated as nonstandard. Those satisfying ⁇ 0 were evaluated as acceptable products.
  • the temperature was raised from 30 ° C. to 200 ° C. at a rate of 500 ° C./min, and then held at 200 ° C. for 2 minutes.
  • the temperature drop was measured from 200 ° C. to 30 ° C. at a rate of 10 ° C./min.
  • the temperature rise measurement was performed from 30 ° C. to 200 ° C. at a rate of 10 ° C./min.
  • Example 1-1 The polyester resin (A) -1 and fine melamine were dry blended at a mixing mass ratio of 80:20, kneaded at 200 ° C. using a 40 mm ⁇ co-directional twin screw extruder, extruded from a T die, and then about The sheet was rapidly cooled with a 40 ° C. casting roll to prepare a sheet having a thickness of 100 ⁇ m. The obtained sheet was evaluated for flame retardancy, tensile strength, tensile elongation, and heat resistance. The results are shown in Table 1.
  • Example 1-2 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in Example 1-1 except that the mixing mass ratio of the polyester resin (A) -1 and fine melamine was set to 70:30. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1-3 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in Example 1-1 except that the mixing mass ratio of the polyester resin (A) -1 and fine melamine was 50:50. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1-4 After blending the polyester resin (A) -2 and fine melamine at a mixing mass ratio of 70:30, a sheet having a thickness of 100 ⁇ m was produced in the same manner as in Example 1-1. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1-5 After blending the polyester resin (A) -3 and fine melamine at a mixing mass ratio of 70:30, a sheet having a thickness of 100 ⁇ m was produced in the same manner as in Example 1-1. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1-6 After blending polyester resin (A) -2, polyester resin (B) -1 and fine melamine at a mixing mass ratio of 50:20:30, a sheet having a thickness of 100 ⁇ m is obtained in the same manner as in Example 1-1. Was made. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1--7 After blending polyester resin (A) -2, polyester resin (B) -1 and fine melamine at a mixing mass ratio of 40:30:30, a sheet having a thickness of 100 ⁇ m is obtained in the same manner as in Example 1-1. Was made. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1-8 After blending polyester resin (A) -2, polyester resin (B) -1 and fine melamine at a mixing mass ratio of 30:40:30, a sheet having a thickness of 100 ⁇ m is obtained in the same manner as in Example 1-1. Was made. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1-9 After blending polyester resin (A) -2, polyester resin (B) -2, and finely divided melamine at a mixing mass ratio of 40:30:30, a sheet having a thickness of 100 ⁇ m is obtained in the same manner as in Example 1-1. Was made. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1-3 After blending polyester resin (B) -2 and finely divided melamine at a mixing mass ratio of 70:30, a sheet having a thickness of 100 ⁇ m was produced in the same manner as in Example 1-1. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example A sheet having a thickness of 100 ⁇ m was produced in the same manner as in 1-1.
  • Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • Example 1 After blending polyester resin (A) -1 and MC-860 at a mixing mass ratio of 70:30 using MC-860 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. instead of melamine A sheet having a thickness of 100 ⁇ m was produced in the same manner as in 1-1. Table 1 shows the results of evaluation similar to Example 1-1 for the obtained sheet.
  • (Discussion) Flame retardant polyester resin composition obtained by mixing polyester resin (A) having a glass transition temperature Tg of ⁇ 20 ° C. to 40 ° C. and a crystal melting temperature Tm of 140 ° C. to 190 ° C. with melamine
  • Tg glass transition temperature
  • Tm crystal melting temperature
  • the flame retardant property, the tensile strength, the tensile elongation, and the heat resistance can all be evaluated as acceptable. I understood that I could do it.
  • melamine can be made flame retardant by blending it with polyester resin (A), whereas melamine derivatives such as melamine cyanurate and melamine polyphosphate are specific polyester resins (A).
  • A polyester resin
  • melamine derivatives such as melamine cyanurate and melamine polyphosphate are specific polyester resins (A).
  • Melamine is generally difficult to use as a flame retardant, but it has been found that it can be used as a flame retardant for certain polyester resins. It has been found that the proportion of melamine is preferably 20 to 60% by mass of the flame retardant polyester resin composition.
  • polyester resin (B) having a glass transition temperature Tg of ⁇ 100 ° C. or more and less than ⁇ 20 ° C. and a crystal melting temperature Tm of 100 ° C. or more and less than 140 ° C.
  • polyester resin (A) and polyester resin By blending so that the mass ratio with the resin (B) is 90:10 to 30:70, all of flame retardancy, tensile strength, tensile elongation, and heat resistance can be evaluated as acceptable. In addition, it has been found that the tensile elongation can be particularly increased.
  • samples with a thickness of 200 ⁇ m or less are judged on the basis of the UL94VTM criteria whether or not the VTM-0, 1 and 2 standards are satisfied.
  • a product satisfying VTM-0 was evaluated as an acceptable product.
  • samples with a thickness exceeding 200 ⁇ m whether or not the standards of VTM-0, 1 and 2 are satisfied is judged based on the UL94V criteria, and those not satisfying VTM-2 are evaluated as nonstandard. Those satisfying ⁇ 0 were evaluated as acceptable products.
  • Polymer resin (A) -2 Product name: Byron GA-1310 manufactured by Toyobo Co., Ltd.
  • polyhydric alcohol component 1,4-butanediol 73 mol%
  • polytetramethylene ether glycol 27 mol%
  • mass average molecular weight 148,000
  • Tg ⁇ 70 ° C.
  • Tm 180 ° C.
  • ⁇ Hm 2.3 J / g
  • Example 2-1 (A) -1, (A) -3, (B) -1, and (C) -1 were dry blended at a mixing mass ratio of 55: 20: 15: 5, and then 40 mm ⁇ co-directional twin screw extrusion After kneading at 200 ° C. using a machine, it was extruded from a T-die and then rapidly cooled with a casting roll at about 40 ° C. to produce a sheet having a thickness of 100 ⁇ m. The obtained sheet was evaluated for flame retardancy, tensile strength, tensile elongation, and stress relaxation characteristics. The results are shown in Table 2.
  • Example 2-2 Example 2-1 except that the mixing mass ratio of the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 was 45: 20: 30: 5 A sheet having a thickness of 100 ⁇ m was produced in the same manner. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-3 Example 2-1 except that the mixing mass ratio of the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 was 15: 20: 55: 5 A sheet having a thickness of 100 ⁇ m was produced in the same manner. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-4 After the polyester resins (A) -2, (A) -3, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 45: 20: 30: 5, Example 2 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in -1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-5 After dry blending (A) -3, (B) -1, and (C) -1 at a mixing mass ratio of 65: 30: 5, a sheet having a thickness of 100 ⁇ m is obtained in the same manner as in Example 2-1. Was made. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-6 After dry blending the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 65: 30: 5, Example 2-1 A sheet having a thickness of 100 ⁇ m was produced in the same manner as described above. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2--7 After the polyester resins (A) -4, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 65: 30: 5, the thickness was determined in the same manner as in Example 2-1. A 100 ⁇ m sheet was prepared. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-8 After the polyester resins (A) -5, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 65: 30: 5, the thickness was determined in the same manner as in Example 2-1. A 100 ⁇ m sheet was prepared. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-9 After the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 48: 20: 30: 2, Example 2 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in -1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-10 Example 2 After dry blending polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 40: 20: 30: 10, Example 2 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in -1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-11 Example 2 After dry blending polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 30: 20: 30: 20, Example 2 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in -1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Example 2-12 After the polyester resins (A) -1, (A) -3, (B) -1 and (C) -2 were dry blended at a mixing mass ratio of 40: 20: 30: 10, Example 2 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in -1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 were blended at a mixing mass ratio of 45: 20: 30: 5. It was compounded at 190 ° C. using a 40 mm ⁇ small-size co-directional twin screw extruder manufactured by Mitsubishi Heavy Industries, and formed into a pellet shape. A plate material having a length of 250 mm, a width of 200 mm and a thickness of 1 mm was injection molded from the obtained pellets using an injection molding machine IS50E (screw diameter: 25 mm) manufactured by Toshiba Machine. The main molding conditions are as follows.
  • Example 2-2 The polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 70: 20: 5: 5, and then Example 2 A sheet having a thickness of 100 ⁇ m was produced in the same manner as in -1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.
  • Polyester resin containing 50 to 90 mol% terephthalic acid as the polyvalent carboxylic acid component and 70 to 100 mol% in total of 1,4-butanediol, ethylene glycol and diethylene glycol as the polyhydric alcohol component It was found that by using (A), excellent tensile strength, tensile elongation and stress relaxation characteristics can be obtained.
  • the polycarboxylic acid component contains isophthalic acid in a proportion of 30 mol% to 50 mol%
  • the polyhydric alcohol component contains ethylene glycol in a proportion of 50 mol% to 100 mol%.
  • the proportion of the phenoxy resin (C) is preferably 1 to 25% by mass of the flame retardant polyester resin composition, particularly 2% by mass or more, more preferably 5% by mass or more, and more preferably 20% by mass or less. In particular, it was found that the content is more preferably 10% by mass or less.
  • melamine can be made flame retardant by blending it with polyester resin (A), whereas melamine derivatives such as melamine cyanurate and melamine polyphosphate are specific polyester resins (A).
  • melamine is generally difficult to use as a flame retardant, but it has been found that it can be used as a flame retardant for certain polyester resins. That is, from the results in Table 2, it does not function as a flame retardant for the polyester resin (A) -6, but functions as a flame retardant for the polyester resins (A) -1 to (A) -5. I understood that.
  • the proportion of melamine (B) is preferably 10 to 60% by mass of the flame retardant polyester resin composition, particularly 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or less. In particular, it was found that 40% by mass or less is more preferable.
  • Flame retardancy ⁇ UL94VTM> The flame retardancy of the flame retardant laminate was evaluated by the UL94 vertical combustion test as follows. That is, using a sample for evaluation having a length of 200 mm ⁇ width of 50 mm (thickness varies depending on each test piece), a combustion test was performed with 5 tests based on the safety standard UL94 vertical combustion test procedure of Underwriters Laboratories. Carried out. Based on the criteria of UL94 vertical combustion test UL94VTM, a laminate satisfying the VTM-0 standard was accepted.
  • the burning time was evaluated according to the following procedure. First, the flame length of the burner was adjusted so as to be 20 mm ⁇ 1 mm, and the flame was in contact with the test laminate for 10 mm ⁇ 1 mm for a predetermined time. Next, the flame of the burner was removed from the test laminate, and the burning time of the test laminate was t1. Next, after completion of the burning time described above, flame contact was performed in the same manner as described above for a predetermined time. Next, the fuel time of the test laminate after removing the smoke contact described above was t2, and the smokeless combustion time of the test laminate was t3.
  • Peel strength Peel strength was measured by using a tensile tester (manufactured by Intesco Corporation: material tester 201X with a thermostatic bath) to measure the peel strength between the A layer and the B layer. The measurement was carried out by a T-type peeling test (JIS K6854-3 1999). An evaluation sample having a width of 10 mm was used, and a T-type peel test was performed at an atmospheric temperature of 23 ° C. and a peel rate of 10 mm / min. The peel strength was 4N / 10 mm or more as acceptable.
  • B layer-B An amorphous sheet having a thickness of 108 ⁇ m was prepared under the same method and conditions as the polyester film A, and then stretched under the same methods and conditions as the polyester film A to obtain a biaxially stretched film having a thickness of 12 ⁇ m.
  • Example 3-1 As a polyester resin (A), Byron GM-443 manufactured by Toyobo Co., Ltd. (terephthalic acid: 26.5 mol%, isophthalic acid: 19.8 mol%, adipic acid: 4.7 mol%, 1,4-butanediol: 50 mol% , Glass transition temperature: 26 ° C., heat of crystal melting ⁇ Hm: 22.8 J / g), as a flame retardant, fine particle size melamine (average particle size 5 ⁇ m) manufactured by Nissan Chemical Co., Ltd., Byron GM-443 and fine particle size melamine Is dry blended at a mixing mass ratio of 80:20, then kneaded at 200 ° C.
  • Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.
  • Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.
  • Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.
  • Example 3-13 As a layer A, a laminate having a thickness of 50 ⁇ m was obtained in the same manner as in Example 3-1, except that the mixing mass ratio of GSPla AD92W and melamine was set to 40:60. Table 3 shows the results of evaluation similar to Example 3-1 for the obtained laminate.
  • Example 3-14 GSPla AD92W and melamine were dry blended at a mixing mass ratio of 60:40, then kneaded at 200 ° C. using a 40 mm diameter same-direction twin screw extruder, extruded from a T die, and layer (B) -A was cast roll.
  • layer (B) -A was cast roll.
  • Example 3-15 A laminate having a thickness of 50 ⁇ m was obtained in the same manner as in Example 3-2 except that B layer-B was used instead of B layer-A. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.
  • Example 3-17 A laminate having a thickness of 50 ⁇ m was obtained in the same manner as in Example 3-10 except that B layer-C was used instead of B layer-A. Table 3 shows the results of evaluation similar to that of Example 3-10 performed on the obtained laminate.
  • Example 3-1 (Comparative Example 3-1) Byron GM-443 and fine particle size melamine were blended at a mixing mass ratio of 60:40, and then a sheet having a thickness of 50 ⁇ m without layering the layer B was obtained in the same manner as in Example 3-1.
  • Table 4 shows the results of evaluation similar to Example 3-1 for the obtained single-layer body.
  • BF013ST aluminum hydroxide manufactured by Nippon Light Metal Co., Ltd. was used in place of the fine particle size melamine.
  • Byron GM-443 and BF013ST were blended at a mixing mass ratio of 60:40, and then the thickness was determined in the same manner as in Example 3-1.
  • Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.
  • Example 3-6 After blending GSPla AD92W and fine particle size melamine at a mixing mass ratio of 60:40, a sheet having a thickness of 50 ⁇ m without layering the layer B was obtained in the same manner as in Example 3-1. Table 4 shows the results of evaluation similar to Example 3-1 for the obtained single-layer body.
  • Example 3-8 MC-600 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. was used instead of melamine, and GSPla AD92W and MC-600 were blended at a mixing mass ratio of 60:40, and then the thickness was determined in the same manner as in Example 3-1. A 50 ⁇ m laminate was obtained. Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.
  • BF013ST aluminum hydroxide manufactured by Nippon Light Metal Co., Ltd. was used in place of melamine, and GSPla AD92W and BF013ST were blended at a mixing mass ratio of 60:40, and then a 50 ⁇ m thick laminate was formed in the same manner as in Example 3-1. Obtained.
  • Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.
  • the flame retardancy of the third flame retardant laminates of Examples 3-1 to 17 passes UL94VTM and is good with less combustion time.
  • the third flame retardant laminates of Examples 3-1 to 15 have sufficient peel strength between the A layer and the B layer, good tensile strength, tensile elongation, and heat resistance. Excellent characteristics.
  • the third flame retardant laminates of Examples 3-16 and 3-17 have good flame retardancy, the heat resistance was not excellent because the B layer-C was used for the B layer. .
  • Comparative Example 3-1 is inferior in tensile strength, tensile elongation, and heat resistance as compared with the third flame retardant laminate because there is no B layer.
  • Comparative Example 3-2 since the content of melamine is as low as 5% by mass, the flame retardancy is inferior to that of the third flame retardant laminate.
  • the polyester resin (A) has a heat of crystal fusion ⁇ Hm of 50 J / g, so that the flame retardancy is inferior to that of the third flame retardant laminate. Since Comparative Example 3-4 uses melamine cyanurate instead of melamine, the flame retardancy is inferior to that of the third flame retardant laminate.
  • Comparative Example 3-5 uses aluminum hydroxide instead of melamine, the flame retardancy is inferior to that of the third flame retardant laminate.
  • Comparative Example 3-6 is inferior in tensile strength, tensile elongation, and heat resistance as compared with the third flame retardant laminate, since there is no B layer as in Comparative Example 3-1.
  • Comparative Example 3-7 since the content of melamine is as small as 5% by mass, the flame retardancy is inferior to that of the third flame retardant laminate.
  • Comparative Example 3-8 uses melamine cyanurate, the flame retardancy is inferior to that of the third flame retardant laminate.
  • Comparative Example 3-9 uses aluminum hydroxide instead of melamine, the flame retardancy is inferior to that of the third flame retardant laminate.
  • the third flame-retardant laminate uses a specific polyester resin and has a specific amount of specific melamine, and thus has good flame resistance and mechanical properties.
  • the third flame-retardant laminate can be suitably used particularly for applications such as flexible flat cables, electrical insulating materials, membrane switch circuit printing base materials, copying machine internal members, planar heating element base materials, and FPC reinforcing plates.
  • a tin-plated copper foil having a thickness of 150 ⁇ m and a width of 10 mm is disposed between the two obtained laminated films (both with the A layer inside), and these are placed on a metal roll (heating) / rubber roll (non-heating).
  • a flat cable was obtained by laminating under conditions of a roll nip pressure of 10 kg / cm (linear pressure) and a laminating speed of 0.5 m / min.
  • Table 5 shows the results of measuring the peel strength between the A layer and the tin-plated copper foil and the heat resistance of the flat cable obtained by the above method.
  • the overall evaluation was evaluated as “x” and all items were acceptable. When it was, the overall evaluation was evaluated as “ ⁇ ”. Moreover, when the obtained flat cable was observed and peeling was seen between A layer and B layer, even if all the said 3 items passed, it decided to evaluate with "x”.
  • Example 4-7 In the configuration of the A layer, two types of Byron GM-443 and 30P are used as the polyester resin (A), and the mixing mass ratio of Byron GM-443, Byron 30P, melamine and E4275 is 35: 20: 40: 5.
  • a laminated film of A 40 ⁇ m) was obtained. The obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1. The results are shown in Table 5.
  • a laminated film of A 40 ⁇ m) was obtained. The obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1. The results are shown in Table 6.
  • a laminated film of A 40 ⁇ m) was obtained. The obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1. The results are shown in Table 6.
  • the obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1. The results are shown in Table 6.
  • a laminated film of A 40 ⁇ m) was obtained. The obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1. The results are shown in Table 7.
  • Example 4 (Comparative Example 4-4)
  • BF013ST aluminum hydroxide manufactured by Nippon Light Metal Co., Ltd.
  • Byron GM-443, BF013ST and E4275 were blended at a mixing mass ratio of 55: 40: 5, and then Example 4-1
  • the obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1.
  • the results are shown in Table 7.
  • the obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1. The results are shown in Table 7.
  • the obtained laminated film was evaluated in the same manner as in Example 4-1, and a flat cable was produced and evaluated in the same manner as in Example 4-1. The results are shown in Table 7.
  • Example 4-1 From the evaluation results of Examples 4-1 to 16, the VTM-0 in the UL94 vertical combustion test was obtained by adding a phenoxy resin together with melamine to a polyester resin having a specific glass transition temperature in the A layer as an adhesive layer. It was found that in addition to the high flame retardant properties that pass the above, excellent heat resistance and excellent adhesion to metal conductors can be obtained. For example, comparing Example 4-1 with Comparative Example 4-1, which does not contain a phenoxy resin, it has been found that the addition of a phenoxy resin significantly increases the adhesion to a metal conductor and also increases the heat resistance. did.
  • Examples 4-4 to 7 use polyester resins (A) having different glass transition temperatures and ⁇ Hm.
  • the polyester resin (A) has higher peel strength at lower temperatures (for example, 0 ° C. or lower) when Tg is lower, and crystallinity when ⁇ Hm is higher. It was found that the heat resistance tends to be high because of the high value.
  • the glass transition temperature of the polyester-based resin (A) is preferably ⁇ 80 ° C. or higher, particularly ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, preferably 30 ° C. or lower, particularly 20 ° C. or lower, In particular, it can be considered that the temperature is preferably 10 ° C.
  • the heat of crystal fusion ⁇ Hm of the polyester resin (A) is preferably 5 to 30 J / g, more preferably 8 J / g or more, more preferably 10 J / g or more, and the upper limit value is particularly 25 J. / G or less, more preferably 20 J / g or less.
  • the glass of the polyester-based resin (B) is preferably 50 to 120 ° C.
  • the lower limit is particularly preferably 55 ° C. or higher, more preferably 60 ° C. or higher
  • the upper limit is particularly 110 ° C. or lower, especially 100 ° C. or lower. It can be considered more preferable.
  • the crystal melting heat ⁇ Hm of the polyester-based resin (B) is preferably 40 to 100 J / g, and the lower limit is particularly preferably 45 J / g or more, more preferably 50 J / g or more, and the upper limit. Can be considered to be 90 J / g or less, more preferably 80 J / g or less.
  • the blending ratio of melamine in the resin composition a constituting the A layer is preferably 20 to 80% by mass, and the lower limit thereof. Is particularly preferably 30% by mass or more, more preferably 40% by mass or more, and the upper limit is particularly preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the proportion of the phenoxy resin in the resin composition a constituting the A layer is preferably 1 to 30% by mass, the lower limit is more preferably 5% by mass or more, and the upper limit is 20%. It can be considered that it is more preferable to be not more than mass%.
  • B layer-2 An amorphous sheet having a thickness of 108 ⁇ m was prepared under the same method and conditions as the B layer-1, and then stretched under the same methods and conditions as the B layer-1 to obtain a biaxially stretched film having a thickness of 12 ⁇ m. It was.
  • fine powdered melamine melamine
  • TMAIC TMAIC manufactured by Nippon Kasei Co., Ltd.
  • a sheet (A layer) having a thickness of 50 ⁇ m was obtained with a casting roll at 55 ° C.
  • the B layer-1 was bonded from the cast roll side and the nip roll side to obtain a laminate having a layer configuration of B-1 / A / B-1 and a thickness of 100 ⁇ m.
  • the laminate was irradiated with radiation ( ⁇ rays) at an irradiation dose of 50 kGy.
  • Table 8 shows the results of evaluating the gel fraction, flame retardancy, tensile strength, elongation, and heat resistance of the obtained laminate.
  • Example 5-2 A laminate was prepared and evaluated in the same manner as in Example 5-1, except that the mixing mass ratio of GSPla AZ91T, fine melamine, and TMAIC was 59: 40: 1. The results are shown in Table 8.
  • Example 5-3 A laminate was prepared and evaluated in the same manner as in Example 5-1, except that the mixing mass ratio of GSPla AZ91T, fine melamine, and TMAIC was 49: 50: 1. The results are shown in Table 8.
  • Example 5-4 A laminate was prepared and evaluated in the same manner as in Example 5-1, except that the mixing mass ratio of GSPla AZ91T, fine melamine, and TMAIC was set to 59.5: 40: 0.5. The results are shown in Table 8.
  • Example 5-5 A laminate was prepared and evaluated in the same manner as in Example 5-1, except that the mixing mass ratio of GSPla AZ91T, fine melamine, and TMAIC was 57: 40: 3. The results are shown in Table 8.
  • Example 5-6 A laminate was produced and evaluated in the same manner as in Example 5-2 except that the thickness of the A layer was 20 ⁇ m. The results are shown in Table 8.
  • Example 5-7 A laminate was prepared and evaluated in the same manner as in Example 5-3 except that the thickness of the A layer was changed to 70 ⁇ m. The results are shown in Table 8.
  • Example 5-8 A laminate was prepared and evaluated in the same manner as in Example 5-2 except that the thickness of the A layer was 30 ⁇ m and B-2 was used as the B layer. The results are shown in Table 8.
  • Example 5-9 GSPla AZ91T, fine melamine, and TMAIC were mixed in the same manner as in Example 5-1, except that the mixing mass ratio was 39: 60: 1, the thickness of layer A was 35 ⁇ m, and layer B-2 was used as layer B.
  • the body was prepared and evaluated. The results are shown in Table 8.
  • Example 5-11 A laminate was prepared and evaluated in the same manner as in Example 5-1, except that the mixing mass ratio of GSPla AD92W, fine melamine, and TMAIC was 49: 50: 1, and the thickness of the A layer was 70 ⁇ m. The results are shown in Table 8.
  • Example 5-12 Example 5-1 except that DA-MGIC (diallyl monoglycidyl isocyanate) manufactured by Shikoku Kasei Kogyo Co., Ltd. was used as the crosslinking agent, and the mixing mass ratio of GSPla AZ91T, fine melamine, and DA-MGIC was 59: 40: 1.
  • a laminate was prepared and evaluated in the same manner as described above. The results are shown in Table 8.
  • Example 5-1 A laminate was prepared and evaluated in the same manner as in Example 5-1, except that the mixing mass ratio of GSPla AZ91T, fine melamine, and TMAIC was 84: 15: 1. The results are shown in Table 8.
  • Example 5-2 A laminate was prepared and evaluated in the same manner as in Example 5-1, except that the mixing mass ratio of GSPla AZ91T, fine melamine, and TMAIC was 39: 60: 1, and the thickness of the A layer was 150 ⁇ m. The results are shown in Table 8.
  • Example 5-4 A layer A similar to that in Example 5-2 was prepared, and a single layer body in which the B layer was not bonded was prepared and evaluated. The results are shown in Table 8.
  • Example 5-5 A laminate was prepared and evaluated in the same manner as in Example 5-3 except that the thickness of the A layer was changed to 10 ⁇ m. The results are shown in Table 8.
  • Example 5-6 Example 5-1 except that MC-860 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. was used instead of melamine, and the mixing mass ratio of GSPla AZ91T, MC-860, and TMAIC was set to 59: 40: 1.
  • the laminate was prepared and evaluated by the method described above. The results are shown in Table 8.
  • Example 5-7 The laminate was prepared in the same manner as in Example 5-1, except that H42S (aluminum hydroxide) manufactured by Showa Denko KK was used instead of melamine, and the mixing mass ratio of GSPlaAZ91T, H42S, and TMAIC was set to 59: 40: 1. Fabrication and evaluation were performed. The results are shown in Table 8.
  • Example 5-9 A laminate was prepared and evaluated in the same manner as in Example 5-3 except that B layer-3 was used as the B layer. The results are shown in Table 8.
  • Comparative Example 5-1 was inferior in flame retardancy because the mass% based on the total laminate of melamine was not within the predetermined range.
  • Comparative Example 5-2 was inferior in tensile strength, tensile elongation, and softening temperature because the mass% with respect to the entire laminate of melamine was not within the predetermined range.
  • Comparative Example 5-3 no crosslinking agent was added, the gel fraction was not within the predetermined range, and the softening temperature was inferior.
  • Comparative Example 5-4 was inferior in tensile strength, tensile elongation, and softening temperature because the B layer was not provided.
  • Comparative Example 5-5 since the thickness of the A layer was thin, the mass% of the entire melamine laminate was low, and the flame retardancy was inferior. Comparative Example 5-6 was inferior in flame retardancy because melamine cyanurate was added instead of melamine. Comparative Example 5-7 was inferior in flame retardancy because aluminum hydroxide was added instead of melamine. In Comparative Example 5-8, since the polyester resin (A) does not have a predetermined glass transition temperature, the tensile elongation was inferior. In Comparative Example 5-9, since the polyester resin (B) does not have a predetermined glass transition temperature, the softening temperature is low and the heat resistance is poor.
  • the laminate according to the fifth embodiment uses a specific polyester resin and uses a specific amount of a specific melamine, and thus has good flame retardancy and heat resistance.
  • wiring cables, flat cables, electrical insulation materials, membrane switch circuit printing base materials, copier internal members, planar heating element base materials, FPC reinforcing plates, etc., produced with the laminate according to the fifth embodiment are difficult. Good flammability, heat resistance and bendability.
  • B layer-A The following two types of films (“B layer-A” and “B layer-B”) were prepared and prepared as the film constituting the B layer.
  • Novapex was kneaded at 260 ° C. with a 40 mm diameter single screw extruder. Then, it extruded from the nozzle
  • Example 6-1 As a polyester resin (A), Byron (registered trademark) GM-480 manufactured by Toyobo Co., Ltd. (terephthalic acid: 45 mol%, sebacic acid: 5 mol%, 1,4-butanediol: 50 mol%, glass transition temperature: ⁇ 2 ° C. , Crystal melting heat quantity ⁇ Hm: 24.6 J / g), Nissan Chemical Co., Ltd. fine melamine (average particle size 5 ⁇ m) is used as a flame retardant, Sakai Kogyo Co., Ltd. PKHB (phenoxy resin) is used as a carbonization accelerator It was.
  • Byron registered trademark
  • GM-480 manufactured by Toyobo Co., Ltd.
  • terephthalic acid 45 mol%
  • sebacic acid 5 mol%
  • 1,4-butanediol 50 mol%
  • glass transition temperature ⁇ 2 ° C.
  • Crystal melting heat quantity ⁇ Hm 24.6 J / g
  • a tin-plated copper foil having a thickness of 150 ⁇ m and a width of 10 mm is placed between the two obtained laminates (both with the A layer inside), and these are made of a metal roll (heating) / rubber roll (non-heating).
  • a flat cable was obtained by laminating under conditions of a roll nip pressure of 10 kg / cm (linear pressure) and a laminating speed of 0.5 m / min.
  • Table 9 shows the results of evaluation of flame retardancy (UL94VTM) for the laminate obtained by the above method, flame retardancy (UL1581VW-1), heat resistance, and bendability for the flat cable.
  • Example 6-5 Example 6-1 except that aluminum hydroxide manufactured by Nacalai Tesque was used as the carbonization accelerator, and the mixing mass ratio of Byron GM-480, melamine and aluminum hydroxide was 50:40:10 in the configuration of layer A.
  • a flat cable was produced in the same manner as in Example 6-1.
  • the same evaluation as in Example 6-1 was performed using the obtained laminate and flat cable. The results are shown in Table 9.
  • a flat cable was produced in the same manner as in Example 6-1. The same evaluation as in Example 6-1 was performed using the obtained laminate and flat cable. The results are shown in Table 9.
  • Comparative Example 6-1 was inferior in flame retardancy of the laminate and the flat cable because the ratio of melamine added to the laminate was small.
  • Comparative Example 6-2 since the ratio of melamine added to the laminate was large, the flat cable was poor in bendability.
  • Comparative Example 6-3 the flame retardant of the laminate was good because the carbonized accelerator was not added to the laminate, but the flame resistance of the flat cable was inferior.
  • Comparative Example 6-4 since the ratio of melamine cyanurate added to the laminate was large and the ratio of melamine was small, the flame resistance of the flat cable was poor, but the flame resistance of the flat cable was inferior.
  • Comparative Example 6-5 although the flame retardance of the laminate was good because ⁇ Hm was not within the range of the present invention for the B layer, the heat resistance of the flat cable was inferior. Comparative Example 6-6 was inferior in flame retardancy, heat resistance and bendability because the polyester resin (A) was not within the scope of the present invention.
  • the laminate according to the sixth embodiment uses a specific polyester resin and uses a specific amount of a specific melamine, so that it has good flame retardancy and a wiring cable is produced. Suitable for.
  • a wiring cable flat cable, electrical insulating material, membrane switch circuit printing base material, copying machine internal member, planar heating element base material, FPC reinforcing plate, etc.
  • a wiring cable flat cable, electrical insulating material, membrane switch circuit printing base material, copying machine internal member, planar heating element base material, FPC reinforcing plate, etc.

Abstract

La présente invention concerne un laminé ignifuge s'avérant excellent quant à ses qualités ignifuges, mécaniques et de surface, sans contenir de composé halogéné ou analogue. L'invention concerne également un câble souple plat. Le laminé ignifuge comporte une couche B sur au moins une face d'une couche A se composant principalement d'un mélange de mélamine et d'une résine de polyester (A) présentant une température de transition vitreuse n'excédant pas 30°C et une enthalpie de fusion du cristal ?Hm n'excédant pas 40J/g. Ce laminé ignifuge est caractérisé en ce que la masse de mélamine représente de 10 à 80% de la masse totale de la couche A. L'invention concerne également un câble souple plat contenant le laminé ignifuge.
PCT/JP2009/001253 2008-03-21 2009-03-19 Composition de résine de polyester ignifuge et laminé ignifuge WO2009116302A1 (fr)

Priority Applications (2)

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CN2009801103214A CN101977989A (zh) 2008-03-21 2009-03-19 阻燃性聚酯类树脂组合物及阻燃性叠层体
KR1020107020291A KR101165652B1 (ko) 2008-03-21 2009-03-19 난연성 폴리에스테르계 수지 조성물 및 난연성 적층체

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JP2008074378 2008-03-21
JP2008-074378 2008-03-21
JP2008250453A JP5368045B2 (ja) 2008-09-29 2008-09-29 金属接着用難燃性樹脂積層体及び配線ケーブル
JP2008-250453 2008-09-29
JP2008312184A JP4856160B2 (ja) 2008-12-08 2008-12-08 難燃性ポリエステル系樹脂組成物
JP2008312185A JP4648450B2 (ja) 2008-12-08 2008-12-08 難燃性ポリエステル系樹脂組成物
JP2008-312184 2008-12-08
JP2008-312185 2008-12-08
JP2009034116A JP2009255543A (ja) 2008-03-21 2009-02-17 難燃性積層体およびそれを用いたフレキシブルフラットケーブル
JP2009-034116 2009-02-17
JP2009-051922 2009-03-05
JP2009051922A JP2010205648A (ja) 2009-03-05 2009-03-05 配線ケーブル用積層体および配線ケーブル
JP2009055760A JP2010208112A (ja) 2009-03-09 2009-03-09 耐熱性難燃積層体および該積層体を利用した配線ケーブル
JP2009-055760 2009-03-09

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Publication number Priority date Publication date Assignee Title
JP6227202B1 (ja) * 2016-07-13 2017-11-08 積水化成品工業株式会社 エステル系エラストマー発泡成形体、その用途及びエステル系エラストマー発泡粒子
JP6253839B1 (ja) * 2016-07-13 2017-12-27 積水化成品工業株式会社 エステル系エラストマー発泡成形体、その用途及びエステル系エラストマー発泡粒子

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JPS5318660A (en) * 1976-08-04 1978-02-21 Unitika Ltd Flame-retardant polyester composition
JPH03215029A (ja) * 1990-01-19 1991-09-20 Matsushita Electric Works Ltd 樹脂成形品
JPH08259787A (ja) * 1995-03-22 1996-10-08 Toyobo Co Ltd 難燃性エラストマー組成物
JPH09296120A (ja) * 1996-04-30 1997-11-18 Toray Ind Inc 難燃性樹脂組成物
JPH1121436A (ja) * 1997-06-30 1999-01-26 Toyobo Co Ltd 難燃性ポリエステルエラストマー組成物
JPH1160924A (ja) * 1997-06-13 1999-03-05 Polyplastics Co 難燃性熱可塑性ポリエステル樹脂組成物
JP2005054017A (ja) * 2003-08-01 2005-03-03 Polyplastics Co 難燃性樹脂組成物

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Publication number Priority date Publication date Assignee Title
JPS5318660A (en) * 1976-08-04 1978-02-21 Unitika Ltd Flame-retardant polyester composition
JPH03215029A (ja) * 1990-01-19 1991-09-20 Matsushita Electric Works Ltd 樹脂成形品
JPH08259787A (ja) * 1995-03-22 1996-10-08 Toyobo Co Ltd 難燃性エラストマー組成物
JPH09296120A (ja) * 1996-04-30 1997-11-18 Toray Ind Inc 難燃性樹脂組成物
JPH1160924A (ja) * 1997-06-13 1999-03-05 Polyplastics Co 難燃性熱可塑性ポリエステル樹脂組成物
JPH1121436A (ja) * 1997-06-30 1999-01-26 Toyobo Co Ltd 難燃性ポリエステルエラストマー組成物
JP2005054017A (ja) * 2003-08-01 2005-03-03 Polyplastics Co 難燃性樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6227202B1 (ja) * 2016-07-13 2017-11-08 積水化成品工業株式会社 エステル系エラストマー発泡成形体、その用途及びエステル系エラストマー発泡粒子
JP6253839B1 (ja) * 2016-07-13 2017-12-27 積水化成品工業株式会社 エステル系エラストマー発泡成形体、その用途及びエステル系エラストマー発泡粒子
JP2018159049A (ja) * 2016-07-13 2018-10-11 積水化成品工業株式会社 エステル系エラストマー発泡成形体、その用途及びエステル系エラストマー発泡粒子

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