WO2009116302A1

WO2009116302A1 - Flame-retardant polyester resin composition and flame-retardant laminate

Info

Publication number: WO2009116302A1
Application number: PCT/JP2009/001253
Authority: WO
Inventors: 田中一也; 北山和彦; 齋藤大嗣
Original assignee: 三菱樹脂株式会社
Priority date: 2008-03-21
Filing date: 2009-03-19
Publication date: 2009-09-24

Abstract

Disclosed is a flame-retardant laminate exhibiting excellent flame retardancy, mechanical characteristics and surface characteristics, without containing a halogen compound and the like. A flexible flat cable is also disclosed. The flame-retardant laminate has a layer B on at least one side of a layer A which is mainly composed of a mixture of melamine and a polyester resin (A) having a glass transition temperature of not more than 30˚C and a crystal melting enthalpy ∆Hm of not more than 40 J/g. The flame-retardant laminate is characterized in that the melamine content is 10-80% by mass relative to the total mass of the layer A. A flexible flat cable containing the flame-retardant laminate is also disclosed.

Description

Flame retardant polyester resin composition and flame retardant laminate

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. However, 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.

As flame retardants for polyester resins, halogen flame retardants such as decabromodiphenyl ether and hexabromodiphenyl have been used. Halogen flame retardants generate harmful gases such as dioxins during combustion. In some cases, 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.

Therefore, the present inventor has focused on nitrogen compounds, particularly melamine, as non-halogen / non-phosphorus flame retardants used in polyester resins.
Regarding the use of 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.

On the other hand, as for 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).

Also, a technology relating to a polyester film in which a resin layer that generates a non-flammable gas is laminated on both sides of the polyester film is disclosed (Japanese Patent Laid-Open No. 2006-35504). However, in the polyester film, although flame retardancy is imparted by installing a flame retardant layer on the surface of the laminated film, the mechanical strength represented by tensile strength, impact strength, etc. is reduced, so that it is practically used. There was a problem that it was difficult to say that it was sufficient technology.

Since melamine starts decomposing at 220 to 250 ° C., there is a problem that melamine is decomposed at a molding temperature of a general polyester resin such as PET or PBT to cause a molding defect.

Therefore, in the present invention, by preparing 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. In addition, 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.

In the 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. .

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described, but the scope of the present invention is not limited to the embodiments described below.

[First Embodiment]
The flame-retardant polyester resin composition according to the first embodiment (hereinafter referred to as “first flame-retardant resin composition”) will be described.

<Composition of the first flame retardant resin composition>
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.

(Polyester resin (1-A))
The polyester resin (1-A) is a polyester resin that is a polycondensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol.
Specific examples of 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.
Among these, 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.

In the polyester resin (1-A), 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.
From this point of view, 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. When the Tg of the polyester resin (1-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 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 ΔHm of the polyester resin (1-A) is preferably 20 to 40 J / g. When ΔHm 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 point of view, the ΔHm 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 μL, 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))
The polyester resin (1-B) is a polyester resin that is a polycondensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol.

Specific examples of 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.
Among these, 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.

In the polyester resin (1-B), 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%.

In the polyester resin (1-B), the total proportion of 1,4-butanediol and ethylene glycol in the polyhydric alcohol component is preferably 65 to 100 mol%. When the polyester resin (1-B) having such a composition is blended with the polyester resin (1-A), the mechanical properties are further improved without impairing the heat resistance of the polyester resin (1-A). can do.
From this point of view, 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%.
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-B) is preferably −100 or higher and lower than −20 ° C. When the Tg of the polyester resin (1-B) is in such a temperature range, the flexibility, particularly the elongation can be increased by blending with the polyester resin (1-A), and the effect is 200 μm in thickness. This is particularly effective for the following thin films. From this viewpoint, 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 ΔHm of the polyester resin (1-B) is preferably 1 J / g or more and less than 20 J / g. If the ΔHm 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 ΔHm 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 μL, 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. However, by blending with the polyester resin (1-A) or the polyester resins (1-A) and (1-B) of the present invention, it 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 μm or less, particularly 0.5 μm to 10 μm. 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 μm or more, particularly preferably 1.5 μm or more, particularly preferably 8.0 μm or less, and particularly preferably 6.0 μm 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.
By treating melamine with these surface treatment agents, the dispersibility of melamine can be improved and the flame retardancy of the first flame retardant resin composition can be further improved.

In addition, 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.
Specific examples of other 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.
Specific examples of 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.
By using these flame retardants and flame retardant aids in combination, the flame retardancy of the first flame retardant resin composition can be further improved.

(Mixing ratio)
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.

When the polyester resin (1-B) is blended, 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).
From such a viewpoint, 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.

(Other ingredients)
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.

Examples of the carbodiimide compound include those having a basic structure represented by the following general formula.
-(N = C = NR-) n-
(In the above formula, n represents an integer of 1 or more. R represents another organic bond unit. In these carbodiimide compounds, the R portion may be aliphatic, alicyclic, or aromatic. .)
Usually, n is appropriately determined between 1 and 50.

Specifically, for example, 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. By mix | blending a carbodiimide compound in this range, the outstanding hydrolysis resistance can be provided, without reducing heat resistance.
From this point of view, 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. . Moreover, it is more preferable that it is 4 mass% or less, and it is preferable that it is 3 mass% or less especially.

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.

<Physical characteristics of the first flame-retardant resin composition>
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.
Regarding 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.
Regarding the flexibility, when 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.
Regarding heat resistance, when the crystal melting heat quantity ΔHm is measured based on JIS K7121, the crystal melting heat quantity (ΔHm) can be adjusted to 1 J / g or more, preferably 3 J / g or more.

<Use of first flame retardant resin composition>
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. Specifically, 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. Or 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.
At this time, considering that 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. Thus, it is preferable to appropriately select the melt extrusion temperature. In consideration of the sublimation temperature of melamine, the molding temperature is preferably adjusted to a temperature range of 160 ° C. or higher and 220 ° C. or lower, particularly less than 210 ° C.

After the pellets produced by the above method are sufficiently dried to remove moisture, a film, a sheet, a plate, or an injection molded product can be molded by the following method.

As film, 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.
In addition to the above methods, 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.

Moreover, 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.
At this time, the layer containing no flame retardant is not particularly limited. For example, in the case of imparting heat resistance, mechanical properties, and surface properties, a layer made of the stretched polyethylene terephthalate film or the like is formed. Is preferred. For the purpose of improving adhesiveness with other materials and using for adhesive tapes, etc., adhesive layer made of rubber, acrylic, vinyl ether or other solvent type or emulsion type adhesives Is preferably formed.
At this time, 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%. By setting the thickness ratio of the flame-retardant polyester resin composition within such a range, it is possible to provide a laminate that does not impair flame retardancy and mechanical properties. From this viewpoint, 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.

As a method of laminating the layer made of the first flame retardant resin composition and the layer not containing the flame retardant, the layers can be laminated by coextrusion, extrusion lamination, heat lamination, dry lamination, or the like.

In the case of co-extrusion, a plurality of layers are combined with resin through a feed block and a multi-manifold die using a plurality of extruders to form a laminate. In order to further impart heat resistance and mechanical strength to the laminate, 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. .

In the case of extrusion lamination, 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.

In the case of thermal lamination and dry lamination, 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 Embodiment]
The flame-retardant polyester resin composition according to the second embodiment (hereinafter referred to as “second flame-retardant resin composition”) will be described.

Simply adding melamine to a polyester-based resin is inferior in stress relaxation characteristics as compared to a vinyl chloride-based resin. For example, when used as a tape material, it has a problem that it is easily peeled off after winding.
Therefore, as a second embodiment of the present invention, in a flame retardant polyester resin composition obtained by blending melamine as a flame retardant into a polyester resin, the melamine is decomposed during molding, resulting in poor molding. In addition, the present invention proposes a new second flame retardant resin composition difficulty that has no stress and has a stress relaxation property such as vinyl chloride.

That is, 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.
Moreover, 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, and excellent stress relaxation characteristics can be obtained. Can do. Moreover, 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.

<Composition of the second flame-retardant resin composition>
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.

(Polyester resin (2-A))
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. Further, as the polyhydric alcohol component, 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%.
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 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. In addition to 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.

It is also possible to use a commercially available polyester resin as the polyester resin (2-A). 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. Among them, a polyester resin containing isophthalic acid in a ratio of 5 mol% or more and less than 30 mol% in the polyvalent carboxylic acid component and ethylene glycol in a ratio of 0 mol% or more and less than 50 mol% in the polyhydric alcohol component ( a-1), the polycarboxylic acid component contains isophthalic acid in a proportion of 30 mol% to 50 mol%, and 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.
By using a mixture of polyester resins (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.

At this time, 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 glass transition temperature Tg of the polyester resin (2-A) is preferably -100 ° C to 40 ° C. When the Tg 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 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 ΔHm of the polyester resin (2-A) is preferably 1 J / g to 30 J / g. If ΔHm 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 ΔHm 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.

(Phenoxy resin)
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 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.

Representative examples of commercially available phenoxy resins include Epicoat (registered trademark) E1256, E4250, E4275 manufactured by Japan Epoxy Resin Co., Ltd., PKHH, PKHC, PKHJ, PKHB, PKFE manufactured by InChem. Among these, from the viewpoint of imparting flame retardancy, Epicoat (registered trademark) E4275 made by Japan Epoxy Resin Co., Ltd., whose main component is bisphenol F, is particularly preferable.

(Mixing ratio)
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. When the blending ratio of the phenoxy resin is within such a range, stress relaxation characteristics and flame retardancy can be improved. From this viewpoint, 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. Moreover, it is preferable that it is 20 mass% or less, and it is still more preferable that it is 10 mass% or less especially.
In particular, when a tape is prepared from the second flame retardant resin composition, 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.

(Other ingredients)
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.
The kind and the compounding quantity of the carbodiimide compound to mix | blend are the same as the carbodiimide compound to mix | blend demonstrated in the 1st flame-retardant resin composition.

In the second flame retardant resin composition, 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.

<Physical characteristics of second flame retardant resin composition>
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.
Regarding 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.
Regarding the flexibility, when 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.
Regarding the stress relaxation characteristics, 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.
Regarding heat resistance, when the crystal melting heat quantity ΔHm is measured based on JIS K7121, the crystal melting heat quantity (ΔHm) can be adjusted to 1 J / g or more, preferably 5 J / g or more.

<Use of second flame retardant resin composition>
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. 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.
Among these, 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.

[Third Embodiment]
Next, a flame retardant laminate (referred to as “third flame retardant laminate”) according to a third embodiment will be described.

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 ΔHm of 40 J / g or less and melamine. A flame retardant laminate having a B layer on at least one surface of the layer, wherein the content of melamine in the total mass of the A layer is 10 to 80% by mass.
Here, “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.
According to the third flame retardant laminate, since a specific polyester resin is used and the A layer has excellent flame retardancy, 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.
In addition, according to the present invention, since 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.

<A layer>
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 ΔHm 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. In addition, the heat of crystal fusion ΔHm 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 ΔHm 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 ΔHm are not particularly limited, but the glass transition temperature is not limited. Is -100 ° C. or higher, and the heat of crystal fusion ΔHm is 0 J / g or higher, excellent adhesive strength with the polyester resin (3-B) can be obtained in all practical temperature ranges.

Examples of the polyester resin (3-A) include aliphatic polyesters, aromatic aliphatic polyesters having a glass transition temperature of 30 ° C. or lower and a crystal melting heat ΔHm 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, sebacic acid, azelaic acid, dopamine Kang acid, 1,3-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acid component such as 1,4-cyclohexane dicarboxylic acid. These polyvalent carboxylic acid components can be used alone or in combination of two or more.

Examples of the polyhydric alcohol component 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 type or in mixture of 2 or more types.

As the aliphatic polyester used in the third flame retardant laminate, a polybutylene succinate-adipate copolymer (manufactured by Mitsubishi Chemical Corporation) 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. "Ecoflex (registered trademark)" series, "Easter Bio (registered trademark)" series manufactured by Eastman Chemicals), and the like.

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. When 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 μl, 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.

As the 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. Specific examples of 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. Specific examples of glycols Examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol. In the third flame retardant laminate, 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. When 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. On the other hand, when 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.

(blend)
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>
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.

Examples of the thermoplastic resin used for the B layer 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.

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))
The 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 ΔHm 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. In addition, the heat of crystal fusion ΔHm 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 ΔHm 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 ΔHm are not particularly limited, but the glass transition temperature is not limited. Is 100 ° C. or less, and the crystal melting heat ΔHm is 90 J / g or less, a laminate having sufficient heat resistance can be obtained.

Specific examples of the 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. When 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. On the other hand, if 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 α-hydroxycarboxylic acid or diol / dicarboxylic acid. However, at this time, it is important that 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. For example, in the 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.

In the ring-opening polymerization method, 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.

Furthermore, as required to improve heat resistance, 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. Furthermore, for the purpose of increasing the molecular weight, 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. By setting the ratio of the layer thickness of the A layer to 20% or more, it is possible to impart sufficient flame retardancy to the flame retardant laminate. On the other hand, by setting the ratio of the layer thickness of the A layer to 70% or less, sufficient mechanical properties can be imparted to the flame retardant laminate.

(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.
The kind of carbodiimide compound to mix | blend is the same as the carbodiimide compound to mix | blend demonstrated in the 1st 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 (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.

Further, various 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. For example, antioxidants, heat stabilizers, UV absorbers, organic particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, flame retardants, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyds Resins, epoxy resins, urea resins, phenol resins, silicone resins, rubber resins, wax compositions, melamine compounds, oxazoline-based crosslinkers, methylolated or alkylolized urea-based crosslinkers, acrylamide, polyamide-based resins, epoxies Resins, isocyanate compounds, aziridine compounds, various silane coupling agents, various titanate coupling agents, and the like can be used.

Among these, slipperiness is achieved when 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 μm, more preferably about 0.05 to 1 μm. Further, 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.

<Physical characteristics of the third flame retardant laminate>
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. When 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.

<Method for producing third flame-retardant laminate>
Next, the manufacturing method of a 3rd flame-retardant laminated body is demonstrated.
Here, although the manufacturing method of a film thru | or sheet-like 3rd flame-retardant laminated body is demonstrated, it is not limited to the example demonstrated below.

As a method of laminating the A layer and the B layer in the third flame retardant laminate, lamination can be performed by coextrusion, extrusion lamination, thermal lamination, dry lamination, or the like.

In the case of coextrusion, 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. Is used to prepare the resin composition by mixing and kneading the raw materials constituting the B layer, extruding the resin composition b with a single screw or twin screw extruder, and feeding the resin through a feed block or multi-manifold die. The third flame-retardant laminate can be formed by merging. Furthermore, in order to impart heat resistance and mechanical strength, 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.

In the case of extrusion lamination, 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. Next, 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.

In the case of thermal lamination and dry lamination, 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.

In order to further improve the adhesion between the A layer and the B layer, 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.
Examples of the anchor coat adhesive used for the anchor coat layer include polyester, polyurethane, acrylic, and PVC-vinyl acetate copolymer systems. Moreover, a roll coat method, a gravure coat method, etc. can be used for application | coating of the adhesive agent for anchor coats. The thickness of the anchor coat layer can be appropriately adjusted, but is preferably in the range of 0.1 μm to 5 μm from the viewpoint of flame retardancy and adhesiveness.

In addition, when extending | stretching a 3rd flame-retardant laminated body, in order to suppress the thermal contraction of a laminated body in any case, it is preferable to heat-set in the state which hold | gripped the sheet | seat after extending | stretching. Usually, in the roll method, heat setting is performed by contacting a heated roll after stretching, and in the tenter method, heat setting is performed in a state where a sheet is held by a clip. The heat setting temperature depends on the type of resin used, but it is preferable to perform the heat setting at a temperature lower by about 10 to 100 ° C. than the melting point of the resin used. Further, for the purpose of further improving the ink adhesion of the polyester resin layers as both outer layers, a surface treatment such as a discharge treatment such as a corona treatment or a flame treatment can be performed.

<Use of third flame retardant laminate>
Since 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.

[Fourth flame retardant laminate]
Next, a flame retardant laminate according to a fourth embodiment (hereinafter referred to as “fourth flame retardant laminate”) will be described.

In the prior art, in order to obtain a high level of flame retardancy that passes VTM-0 in the UL94 vertical combustion test, it is necessary to add a large amount of flame retardant to the adhesive layer. There existed problems, such as adhesiveness with a metal falling. Moreover, when it was going to reduce the quantity of the flame retardant mix | blended with an adhesive bond layer, it was necessary to contain a flame retardant in layers other than an adhesive layer.
Therefore, in view of such problems of the conventional technology, 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.
That is, 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. A resin laminate having a B layer composed of a resin composition b mainly composed of a polyester resin (4-B) having a crystal melting heat ΔHm of 40 to 100 J / g, and constituting the A layer a flame retardant resin laminate for metal bonding, wherein the proportion of melamine in a is 20 to 80% by mass and the proportion of phenoxy resin in the resin composition a is 1 to 30% by mass The body is proposed.

According to the fourth flame-retardant laminate, the specific polyester resin constituting the adhesive layer (A layer) mainly improves the adhesion between melamine for improving flame retardancy and mainly metal. By blending with the phenoxy resin for the purpose, the flame retardancy can be increased, and the adhesiveness between the adhesive layer (A layer) and the metal can be significantly increased. In addition, 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). By doing so, adhesiveness with a metal can be improved, without reducing a flame retardance.
Moreover, since melamine generates a nonflammable gas at the time of combustion, not only the adhesive layer can be made flame retardant, but also the outer layer (B layer) not containing a flame retardant can be made flame retardant. Therefore, the flame retardance of the entire laminate can be particularly enhanced.
In addition, by combining phenoxy resin and melamine in the polyester resin (4-A), a synergistic effect can be obtained without canceling each other's characteristics.

Now, 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.
Here, “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.

<A layer>
In the fourth flame retardant laminate, 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))
It is important that the 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 ΔHm of 5 to 30 J / g. When the heat of crystal melting ΔHm 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.
From this viewpoint, the heat of crystal fusion ΔHm 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.

As the 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.

Examples of the aliphatic polyester used as the polyester resin (4-A) 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 One, two or more polyhydric alcohols of no, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A and tetrabromobisphenol A-bis (2-hydroxyethyl ether); Copolymer polyesters comprising:

More specifically, 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, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid;
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-cyclohexane One or more polyhydric alcohols of dimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A and tetrabromobisphenol A-bis (2-hydroxyethyl ether); A copolymer consisting of Riesuteru can be mentioned.

More specifically, 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).

Among these, at least one polyvalent carboxylic acid component selected from succinic acid, adipic acid, terephthalic acid and isophthalic acid, 1,4-butanediol, 1,6-hexanediol, ethylene glycol and polytetramethylene ether 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 | molding defect by the viscosity of resin being too high will not generate | occur | produce.
From this viewpoint, the weight average molecular weight of the aliphatic polyester and the aromatic aliphatic polyester is particularly preferably 80,000 or more, and more preferably 100,000 or more. Also, it is particularly preferably 300,000 or less, and more preferably 250,000 or less.

Examples of the polyester hot melt resin used as the polyester resin (4-A) include a resin composition containing as a main component a polyester hot melt resin that is a polycondensation polymer of dibasic acid and glycol. .
Specific examples of 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. Specific examples of glycols Examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol.
Among the above, 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.
Examples of commercially available 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 | occur | produce in a shaping | molding process is low.
From this viewpoint, the mass average molecular weight of the polyester-based hot melt adhesive is particularly preferably 25,000 or more, and more preferably 30,000 or more. Further, it is particularly preferably 110,000 or less, and more preferably 100,000 or less.

(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.

(Phenoxy resin)
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.

(Mixing ratio)
It is important that 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.

Regarding the blending amount of the phenoxy resin, it is important that 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.

<B layer>
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 ΔHm of 40 to 100 J / g. By satisfying this condition, a laminate having excellent heat resistance can be provided.

It is important that the glass transition temperature of the polyester resin (4-B) is 50 to 120 ° C. as described above. When 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.
From such a viewpoint, the glass transition temperature of the polyester resin (4-B) is preferably 55 ° C. or higher, and more preferably 60 ° C. or higher. Moreover, it is preferable that it is 110 degrees C or less, and it is still more preferable that it is 100 degrees C or less especially.

It is important that the heat of crystal fusion ΔHm of the polyester resin (4-B) is 40 to 100 J / g as described above. When the heat of crystal melting ΔHm of the polyester resin (4-B) is 40 to 100 J / g, problems such as deformation during secondary processing do not occur.
From this viewpoint, the heat of crystal fusion ΔHm 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.

Specific examples of the polyester resin (4-B) include aromatic polyesters obtained by polymerizing polyvalent carboxylic acids and polyhydric alcohols, and aliphatic polyesters such as lactic acid resins.

In this case, 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, dodecanedioic acid, 1,3-cyclohex Njikarubon acid, aliphatic dicarboxylic acid component such as 1,4-cyclohexane dicarboxylic acid. These polyvalent carboxylic acid components can be used alone or in combination of two or more.

Examples of the polyhydric alcohol component include diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 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-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), etc. . These polyhydric alcohol components can be used individually by 1 type or in mixture of 2 or more types.

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.

<Other ingredients>
In the fourth flame-retardant laminate, 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.

<Layer thickness>
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%. By setting the ratio of the layer thickness of the A layer to 20% or more, it is possible to impart sufficient flame retardancy to the fourth flame retardant laminate. On the other hand, by setting the ratio of the layer thickness of the A layer to 70% or less, sufficient mechanical properties can be imparted to the fourth flame retardant laminate.
From this viewpoint, the ratio of the layer thickness of the A layer to the total layer thickness of the fourth flame retardant laminate 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.

In addition, the 4th flame-retardant laminated body may be provided with layers other than A layer and B layer. For example, 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.

<Peel strength>
In the fourth flame-retardant laminate, 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.
Further, when the A layer of the fourth flame retardant laminate is bonded to a metal, for example, assuming that a wiring cable is produced, the peel strength between the A layer and the metal (particularly tin-plated copper foil) is 23 ° C. 5 N / cm or more, particularly preferably 6 N / cm or more, and particularly preferably 7 N / cm or more.
In particular, if 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.

<Manufacturing method>
The fourth flame retardant laminate can be produced in the same manner as the third flame retardant laminate described above.

<Application>
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.

In addition, 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. In addition to the above, it can be suitably used for other applications where flame retardancy and metal adhesion are required. For example, a reinforcement board and a label are mentioned. Here, the reinforcing plate refers to a plate attached to the end of the wiring cable.

[Fifth flame retardant laminate]
Next, a flame retardant laminate according to a fifth embodiment (hereinafter referred to as “fifth flame retardant laminate”) will be described.

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. Is a laminate having a B layer composed mainly of a polyester resin (5-B) at 60 ° C. or higher, the gel fraction of the laminate being 15% by mass or more and 55% by mass or less, and 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. or higher. Excellent adhesion strength with the B layer comprising (5-B) can be obtained.
Further, when the heat of crystal fusion ΔHm of the polyester resin (5-A) is 40 J / g or less, preferably 35 J / g or less, more preferably 30 J / g or less, the adhesive strength with the B layer can be further improved. Can do.

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.

Examples of the aromatic aliphatic polyester 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. When 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 μl, 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.

As the 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. Specific examples of 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. Specific examples of glycols Examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol. In the fifth flame retardant laminate, 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. When 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. On the other hand, when 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.

When using surface-treated melamine, 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. When the content is 10% by mass or more, 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.

(Crosslinking 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. . Specifically, 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.

As a compounding quantity of the said crosslinking agent, it is preferable that 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. By blending the cross-linking agent in such a range, a sufficient gel fraction can be obtained, and excellent heat resistance can be imparted to the laminate.

(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.
Further, when the lower limit value of the heat of crystal fusion ΔHm 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.

Here, 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.

Examples of the polyhydric alcohol component 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 combination of two or more.

Specific examples of the 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. When 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. On the other hand, if 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.

<Layer structure>
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.

<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.
The kind of carbodiimide compound to mix | blend is the same as the carbodiimide compound to mix | blend demonstrated in the 1st flame retardant resin composition.

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 | blend in a ratio, and it is more preferable to mix | blend in the ratio of 1 to 5 mass parts. 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.

Further, 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. For example, antioxidants, heat stabilizers, UV absorbers, organic particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, flame retardants, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyds Resins, epoxy resins, urea resins, phenol resins, silicone resins, rubber resins, wax compositions, melamine compounds, oxazoline-based crosslinkers, methylolated or alkylolized urea-based crosslinkers, acrylamide, polyamide-based resins, epoxies Resins, isocyanate compounds, aziridine compounds, various silane coupling agents, various titanate coupling agents, and the like can be used.

Among these, slipperiness is achieved when 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 μm or more and 5 μm or less, and more preferably 0.05 μm or more and 1 μm or less. Moreover, 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 | blend in the ratio of the weight% or less, and it is more preferable to mix | blend in the ratio of 0.1 to 10 weight%.
If the amount added is too large, moldability may decrease.

<Manufacturing method>
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.

In the fifth flame retardant laminate, in order to impart heat resistance to the flame retardant laminate obtained by the above method, it is important to perform crosslinking by irradiation with ionizing radiation. Examples of the ionizing radiation include ultraviolet rays / electron beams / α rays, β rays, γ rays, neutron rays, etc. In order to advance the crosslinking more efficiently, it is preferable to use electron rays and γ rays. 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. By irradiating with ionizing radiation at an irradiation dose in such a range, crosslinking proceeds sufficiently, and excellent heat resistance can be imparted to the fifth flame-retardant laminate. The irradiation time is not particularly limited, and it is sufficient to perform a time for sufficiently completing the crosslinking reaction of the laminate.

At this time, it is important that 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%. When 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.

<Application>
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.

In addition, 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).
When the blending amount of melamine is not known in advance, 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. In addition, when the blending amount of the inorganic substance is not known in advance, the addition amount of the inorganic material may be calculated from the sum of the inorganic elements by elemental analysis.

[Sixth flame retardant laminate]
Next, a flame retardant laminate according to a sixth embodiment (hereinafter referred to as “sixth flame retardant laminate”) will be described.

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. On the A layer, 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 ΔHm of 40 to 100 J / g. A layered body, the proportion of melamine in the resin composition a constituting the layer A is 20 to 80% by mass, and the proportion of carbonization accelerator in the resin composition a is 1 to 30 It is a laminated body for a wiring cable, characterized by being mass%.

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). . In addition, 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. Furthermore, by blending melamine and a carbonization accelerator, carbonization of the resin proceeds rapidly during combustion, and a wiring cable laminate capable of satisfying the UL1581VW-1 standard can be provided.

Now, 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.
Here, “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.

<A layer>
In the sixth flame-retardant laminate, 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.

(Polyester resin (6-A))
It is important that 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 ΔHm of 5 to 30 J / g. When the heat of crystal melting ΔHm 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.
From this viewpoint, the heat of crystal fusion ΔHm of the polyester-based resin (6-A) is preferably 8 J / g or more, and more preferably 10 J / g or more. Moreover, it is preferable that it is 25 J / g or less, and it is further more preferable that it is 20 J / g or less.

As the 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.

Examples of the aliphatic polyester used as the polyester resin (6-A) 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) And a copolyester comprising:

Examples of the aromatic aliphatic polyester used as the polyester resin (6-A) 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-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-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A and tetrabro Mention may be made of a copolyester composed of one or more of polybisalcohol A-bis (2-hydroxyethyl ether).

More specifically, 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).

Among these, at least one polyvalent carboxylic acid component selected from succinic acid, adipic acid, terephthalic acid and isophthalic acid, 1,4-butanediol, 1,6-hexanediol, ethylene glycol and polytetramethylene ether 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 | molding defect by the viscosity of resin being too high will not generate | occur | produce.
From this viewpoint, the mass average molecular weight of the aliphatic polyester and the aromatic aliphatic polyester is preferably 80,000 or more, and more preferably 100,000 or more. Moreover, it is preferable that it is 300,000 or less, and it is further more preferable that it is 250,000 or less.

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 μL, 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.

(Carbonization accelerator)
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. And the like. Among these, in particular, by using a phenoxy resin, in addition to an excellent carbonization promoting effect, the adhesive strength with a metal can also be improved. In addition, 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.

<Combination ratio>
In the sixth flame-retardant laminate, it is important that 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.

It is important that the blending ratio of the carbonization accelerator in the resin composition a constituting the A layer is 1 to 30% by mass. When 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. On the other hand, if the blending ratio of melamine is 30% 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 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.

<B layer>
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 ΔHm of 40 to 100 J / g. By satisfying this condition, a laminate having excellent heat resistance can be provided.

It is important that the glass transition temperature of the polyester resin (6-B) is 50 to 120 ° C. as described above. When 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.
From this viewpoint, the glass transition temperature of the polyester resin (6-B) is preferably 55 ° C. or higher, and more preferably 60 ° C. or higher. Moreover, it is preferable that it is 110 degrees C or less, and it is still more preferable that it is 100 degrees C or less especially.

It is important that the heat of crystal fusion ΔHm of the polyester resin (6-B) is 40 to 100 J / g as described above. When the heat of crystal fusion ΔHm of the polyester resin (6-B) is 40 to 100 J / g, problems such as deformation during secondary processing do not occur.
From this point of view, the heat of crystal fusion ΔHm 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.

Specific examples of the polyester resin (6-B) include aromatic polyesters obtained by polymerizing polyvalent carboxylic acids and polyhydric alcohols, and aliphatic polyesters such as lactic acid resins.

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.

<Other ingredients>
In the sixth flame-retardant laminate, 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 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.

To the A layer and B layer constituting the sixth flame retardant laminate, an additive for imparting a function, a different resin, etc. are added within a range not inhibiting the effect of the sixth flame retardant laminate. May be. Examples of 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. Examples of different resins include polyolefin resins, styrene resins, polyolefin resins, acrylic resins, polycarbonate resins, polyamide resins, and the like.

<Layer thickness>
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%. By setting the ratio of the layer thickness of the A layer to 20% or more, it is possible to impart sufficient flame retardancy to the sixth flame retardant laminate. On the other hand, by setting the ratio of the layer thickness of the A layer to 70% or less, sufficient mechanical properties can be imparted to the sixth flame-retardant laminate.
From this viewpoint, the ratio of the layer thickness of the A layer to the total layer thickness of the sixth flame retardant laminate 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.

In the sixth flame-retardant laminate, the A layer thickness is usually 10 μm or more, preferably 20 μm or more, more preferably 40 μm or more, and usually 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less. The B layer thickness is usually 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and is usually 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less.

Note that the sixth flame retardant laminate may include a layer other than the A layer and the B layer. For example, 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.

<Flame retardance>
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.

<Manufacturing method>
The sixth flame retardant laminate can be produced in the same manner as the third flame retardant laminate described above.

<Application>
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.
In particular, 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.

[Explanation of terms]
In the present invention, 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. Although 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. For example, 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.

Further, in this specification, when “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.

In general, "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. (Japanese Industrial Standards JISK6900), “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. However, 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. For example, 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.
(1) 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.
(2) 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.
(3) The glass transition temperature and the heat of crystal melting are read from the thermogram obtained by the measurement of (2).

Examples and comparative examples corresponding to the first and second embodiments (flame retardant polyester resin compositions) and the third to sixth embodiments (flame retardant laminates) described above, respectively. Will be described.
However, the scope of the present invention is not limited to the following examples.

[Example and Comparative Example of First Embodiment]
First, examples and comparative examples according to the first embodiment will be described.

(1) Flame retardance When the thickness is 200 μm or less, an evaluation sample having a length of 200 mm × width 50 mm, and when the thickness exceeds 200 μm, the length is 127 mm × width 13 mm (thickness varies depending on each test piece). Test using the sample for evaluation based on the procedures of Underwriters Laboratories Safety Standard UL94 Thin Material Vertical Combustion Test (when the sample thickness is 200 μm or less) and UL94 Vertical Combustion Test (when the sample thickness exceeds 200 μm) A combustion test was carried out at 5 times, and the state of combustion (particularly, the presence or absence of dripping material during combustion) was observed and the combustion time (total combustion time of 5 tests) was measured.
In the UL94 vertical combustion test, samples with a thickness of 200 μm 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. For samples with a thickness exceeding 200 μm, 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.

(2) Tensile strength and tensile elongation Using an evaluation sample having a length of 200 mm and a width of 20 mm, the tensile break strength and the tensile break elongation were measured based on JIS C 2318. The strength and elongation at break were measured, and the average value at n = 5 was determined. Measurement was performed at an ambient temperature of 23 ° C., a relative humidity of 50%, a pulling speed of 200 mm / min, and a gripping interval of 100 mm, and the strength and elongation at break were measured, and the average value at n = 5 was obtained.
A tensile strength of 10 MPa or more and a tensile elongation of 10% or more were evaluated as acceptable.

(3) Heat of crystal melting (ΔHm)
Based on JIS K7121, the crystal melting heat ΔHm of the polyester resin was measured using DSC-7 manufactured by Perkin Elmer Co., Ltd. The measurement procedure is shown below.

a. 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.
b. Next, the temperature drop was measured from 200 ° C. to 30 ° C. at a rate of 10 ° C./min.
c. Furthermore, the temperature rise measurement was performed from 30 ° C. to 200 ° C. at a rate of 10 ° C./min.

C. From the thermogram obtained in the above process, the heat of crystal melting (ΔHm) was read.

(4) Heat resistance One end of an evaluation sample having a length of 200 mm and a width of 20 mm is fixed and held vertically in a baking test apparatus (DKS-5S manufactured by Daiei Kagaku Seisaku Seisakusho) at 140 ° C for 1 hour. Heated. The appearance of the sample after heating was visually observed. A sample having no significant change compared to that before heating was marked with ◯, and a sample showing shrinkage, wrinkles, significant deformation, etc. compared with before heating was marked with ×.

<Raw material>
Next, the raw materials used in Examples and Comparative Examples, that is, polyester resin (A), polyester resin (B), and melamine will be described.

[Polyester resin (A) -1]
Product name: Byron Byron GM-443 manufactured by Toyobo Co., Ltd.
Composition: polycarboxylic acid component = 53 mol% terephthalic acid, 38 mol% isophthalic acid, 9 mol% adipic acid, polyhydric alcohol component = 100 mol% 1,4-butanediol
Physical property values: mass average molecular weight = 47,000, Tg = 26 ° C., Tm = 145 ° C., ΔHm = 22.8 J / g

[Polyester resin (A) -2]
Product name: Byron GA-1300 manufactured by Toyobo Co., Ltd.
Composition: polycarboxylic acid component = terephthalic acid 66 mol%, isophthalic acid 10 mol%, adipic acid 24 mol%, polyhydric alcohol component = 1,4-butanediol 100 mol%
Physical property values: mass average molecular weight = 50,000, Tg = −6 ° C., Tm = 167 ° C., ΔHm = 23.7 J / g

[Polyester resin (A) -3]
Product name: Byron GA-1310 manufactured by Toyobo Co., Ltd.
Composition: polyvalent carboxylic acid component = 71 mol% terephthalic acid, 29 mol% isophthalic acid, polyhydric alcohol component = 1,4-butanediol = 100 mol%
Physical property values: mass average molecular weight = 56,000, Tg = 27 ° C., Tm = 179 ° C., ΔHm = 24.5 J / g

[Polyester resin (B) -1]
Product name: Byron 30P manufactured by Toyobo Co., Ltd.
Composition: polycarboxylic acid component = terephthalic acid 54 mol%, sebacic acid 46 mol%, polyhydric alcohol component = 1,4-butanediol 82 mol%, ethylene glycol = 18 mol%
Physical property values: mass average molecular weight = 96,000, Tg = −28 ° C., Tm = 125 ° C., ΔHm = 2.0 J / g

[Polyester resin (B) -2]
Product name: Byron Byron GM-913 manufactured by Toyobo Co., Ltd.
Composition: polycarboxylic acid component = terephthalic acid 66 mol%, isophthalic acid 34 mol%, polyhydric alcohol component = 12,4-butanediol 82 mol%, polytetramethylene ether glycol 18 mol%
Physical property values: mass average molecular weight = 100,000, Tg = −70 ° C., Tm = 126 ° C., ΔHm = 10.2 J / g

[melamine]
Fine melamine produced by Nissan Chemical Industries (average particle size 5μm, no surface treatment)

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 mmφ 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 μm. 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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.

(Comparative Example 1-1)
After blending the polyester resin (A) -1 and fine melamine at a mixing mass ratio of 90:10, a sheet having a thickness of 100 μm 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.

(Comparative Example 1-2)
After blending the polyester resin (A) -1 and fine melamine at a mixing mass ratio of 30:70, a sheet having a thickness of 100 μm 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.

(Comparative 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 μm 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.

(Comparative Example 1-4)
After blending polyester resin (A) -1 and PHOSMEL-200 at a mixing mass ratio of 70:30 using PHOSMEL-200 (melamine polyphosphate) manufactured by Nissan Chemical Industries, Ltd. instead of melamine, Example A sheet having a thickness of 100 μm 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.

(Comparative Example 1-5)
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 μm 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 In the case where the ratio of melamine in the flame retardant polyester resin composition is 20 to 60% by mass, 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.

In addition, 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). The result that can not be flame retardant.
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.

Further, a 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. is referred to as 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.

[Example and Comparative Example of Second Embodiment]
Next, examples and comparative examples according to the second embodiment will be described.

(1) Flame retardance When the thickness is 200 μm or less, the sample for evaluation of length 200 mm × width 50 mm (thickness varies depending on each test piece), when the thickness exceeds 200 μm, length 127 mm × width 13 mm ( Underwriters Laboratories safety standard UL94 thin material vertical combustion test (when sample thickness is 200 μm or less) and UL94 vertical combustion test (sample thickness is 200 μm) Based on the above procedure, a combustion test is performed at a test count of 5 times, the state of combustion (especially the presence or absence of drops during combustion) is observed, and the combustion time (total combustion time of the test count of 5 times) Was measured.
In the UL94 vertical combustion test, samples with a thickness of 200 μm 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. For samples with a thickness exceeding 200 μm, 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.

(2) Tensile strength and tensile elongation Using a sample for evaluation of length 200 mm × width 20 mm (thickness varies depending on each test piece), measurement of tensile strength and elongation at break based on JIS C 2318 went. The strength and elongation at break were measured, and the average value at n = 5 was determined. Measurement was performed at an ambient temperature of 23 ° C., a relative humidity of 50%, a pulling speed of 200 mm / min, and a gripping interval of 100 mm, and the strength and elongation at break were measured, and the average value at n = 5 was obtained.
A tensile strength of 10 MPa or more and a tensile elongation of 10% or more were evaluated as acceptable.

(3) Stress relaxation characteristics Using an evaluation sample having a length of 200 mm × width of 20 mm (thickness varies depending on each test piece), based on JIS C 2318, the ambient temperature is 23 ° C., the relative humidity is 50%, and the tensile speed is 200 mm / From (1)-(II) / (II) / (II) / (II), the stress (I) when pulled by 10% based on the gripping interval at the gripping interval of 100 mm and the stress (II) after holding for 5 minutes The stress relaxation rate was measured by the formula (I)} × 100 (%).
A stress relaxation rate of 50% or more was evaluated as acceptable. In addition, about what fractured | ruptured the sample when it pulled 10%, it evaluated that it was unmeasurable.

(4) Calorie heat of fusion Measurement and evaluation were performed in the same manner as in the example according to the first embodiment.

<Raw material>
Next, the raw materials used in Examples and Comparative Examples, that is, polyester resin (A), melamine, and polyester resin (B) will be described.

[Polyester resin (A) -1]
Product name: Byron GA-1300 manufactured by Toyobo Co., Ltd.
Composition: polycarboxylic acid component = terephthalic acid 66 mol%, isophthalic acid 10 mol%, adipic acid 24 mol%, polyhydric alcohol component = 1,4-butanediol 100 mol% Physical properties: mass average molecular weight = 50,000, Tg = − 6 ° C., Tm = 167 ° C., ΔHm = 23.7 J / g

[Polyester resin (A) -2]
Product name: Byron GA-1310 manufactured by Toyobo Co., Ltd.
Composition: polyvalent carboxylic acid component = 71 mol% terephthalic acid, 29 mol% isophthalic acid, polyhydric alcohol component = 1,4-butanediol = 100 mol%
Physical property values: mass average molecular weight = 56,000, Tg = 27 ° C., Tm = 179 ° C., ΔHm = 24.5 J / g

[Polyester resin (A) -3]
Product name: Byron 30P manufactured by Toyobo Co., Ltd.
Composition: polycarboxylic acid component = terephthalic acid 54 mol%, sebacic acid 46 mol%, polyhydric alcohol component = 1,4-butanediol 82 mol%, ethylene glycol = 18 mol%
Physical property values: mass average molecular weight = 96,000, Tg = −28 ° C., Tm = 125 ° C., ΔHm = 2.0 J / g

[Polyester resin (A) -4]
Product name: Polyester SP160 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
Composition: polycarboxylic acid component = terephthalic acid = 62 mol%, adipic acid = 19 mol%, sebacic acid = 19 mol%, polyhydric alcohol component = 1,4-butanediol = 100 mol%,
Physical property values: mass average molecular weight = 82,000, Tg = −20 ° C., Tm = 150 ° C., ΔHm = 26.0 J / g

[Polyester resin (A) -5]
Product name: Byron GM-470 manufactured by Toyobo Co., Ltd.
Composition: polyvalent carboxylic acid component = terephthalic acid 86 mol%, adipic acid 14 mol%, polyhydric alcohol component = 1,4-butanediol 87 mol%, 1,6-heptanediol 13 mol%
Physical property values: mass average molecular weight = 58,000, Tg = 20 ° C., Tm = 185 ° C., ΔHm = 27.0 J / g

[Polyester resin (A) -6]
Product name: Peroprene P40B manufactured by Toyobo Co., Ltd.
Composition: Polycarboxylic acid component = terephthalic acid = 100 mol%, polyhydric alcohol component = 1,4-butanediol 73 mol%, polytetramethylene ether glycol 27 mol%
Physical property values: mass average molecular weight = 148,000, Tg = −70 ° C., Tm = 180 ° C., ΔHm = 2.3 J / g

[Melamine (B) -1]
Fine melamine produced by Nissan Chemical Industries (average particle size 5μm, no surface treatment)

[Phenoxy resin (C) -1]
Product name: E4275 manufactured by Japan Epoxy Resin Co., Ltd.
Composition: bisphenol A / bisphenol F = 25 mol% / 75 mol%

[Phenoxy resin (C) -2]
Product name: Japan Epoxy Resin E1256
Composition: Bisphenol A = 100 mol%

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 mmφ 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 μm. 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 μm 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 2-13)
As in Example 2-2, 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 mmφ 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.
1) Temperature conditions: Cylinder temperature (190 ° C) Mold temperature (30 ° C)
2) Injection conditions: Injection pressure (115 MPa) Holding pressure (55 MPa)
3) Measurement conditions: Screw rotation speed (65 rpm) Back pressure (15 MPa)
Table 2 shows the results obtained by cutting out samples for evaluation from the obtained molded products and performing the same evaluation as in Example 2-1.

(Comparative Example 2-1)
After the polyester resins (A) -1, (A) -3, and (B) -1 were dry blended at a mixing mass ratio of 50:20:30, the thickness was determined in the same manner as in Example 2-1. A 100 μm sheet was prepared. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.

(Comparative 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 μm 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.

(Comparative Example 2-3)
After the polyester resins (A) -1, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 35:25:40, the thickness was determined in the same manner as in Example 2-1. A 100 μm sheet was prepared. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.

(Comparative Example 2-4)
After the polyester resins (A) -1, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 25: 70: 5, the thickness was determined in the same manner as in Example 2-1. A 100 μm sheet was prepared. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.

(Comparative Example 2-5)
MC-860 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. was used instead of melamine, and the polyester resins (A) -1, (A) -3, (C) -1 and MC-860 were mixed in a mass ratio. After dry blending at a ratio of 45: 20: 5: 30, a sheet having a thickness of 100 μm was produced in the same manner as in Example 2-1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.

(Comparative Example 2-6)
Instead of melamine, H42S (stearic acid-treated aluminum hydroxide) manufactured by Showa Denko KK was used, and (A) -1, (A) -3, (C) -1, and H42S were mixed at a mass ratio of 45: 20: 5. : After dry blending at a ratio of 30, a sheet having a thickness of 100 μm was produced in the same manner as in Example 2-1. Table 2 shows the results of evaluation similar to Example 2-1 for the obtained sheet.

(Comparative Example 2-7)
Instead of the polyester resin (A), a polyester resin (A) -6 (Perprene P40B) is used, and (A) -6, (B) -1 and (C) -1 are mixed at a mass ratio of 65: After dry blending at a ratio of 25:10, a sheet having a thickness of 100 μm was produced in the same manner as in Example 2-1. 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.

Among them, a polyester resin containing isophthalic acid in a ratio of 5 mol% or more and less than 30 mol% in the polyvalent carboxylic acid component and ethylene glycol in a ratio of 0 mol% or more and less than 50 mol% in the polyhydric alcohol component ( a-1), the polycarboxylic acid component contains isophthalic acid in a proportion of 30 mol% to 50 mol%, and the polyhydric alcohol component contains ethylene glycol in a proportion of 50 mol% to 100 mol%. It has been found that by using a mixture with the polyester resin (a-2), further excellent tensile strength, tensile elongation and stress relaxation characteristics can be obtained.

It is confirmed that the stress relaxation property of the polyester resin (A) can be improved by adding the phenoxy resin (C) to the polyester resin (A), and the flame retardancy can be further improved. did it.
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.

In addition, 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). The result that can not be flame retardant.
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.

[Example and Comparative Example of Third Embodiment]
First, examples and comparative examples according to the third embodiment will be described.
The results shown in the following examples were evaluated by the following methods.

(1) 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.

<Burning time>
In the UL94VTM test, 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.

In addition, the burning time described in Table 3 and Table 4 describes the total time of t1, t2, and t3 of the five test laminates having the configurations described in the examples and comparative examples (VL94VTM). Test compliance).

(2) 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.

(3) Tensile strength and tensile elongation Using a sample for evaluation having a length of 200 mm x a width of 15 mm (thickness varies depending on each test piece), the tensile strength at break and the tensile elongation at break were measured based on JIS C 2318. went. The strength and elongation at break were measured, and the average value at n = 5 was determined. Measurement was performed at an ambient temperature of 23 ° C., a relative humidity of 50%, a pulling speed of 100 mm / min, and a gripping interval of 100 mm, and the strength and elongation at break were measured, and the average value at n = 5 was obtained. The tensile strength was 80 MPa or more, and the tensile elongation was 50% or more.

(4) Heat resistance A sample for evaluation having a length of 100 mm × width of 100 mm (thickness varies depending on each test piece) is allowed to stand in a baking test apparatus (DKS-5S manufactured by Daiei Kagaku Seisakusho Co., Ltd.). Heated for minutes. The external appearance of the sample after heating was visually observed, and the sample that did not change from that before heating was evaluated as “◯”, and the sample that caused shrinkage, wrinkles, deformation, etc. was evaluated as “X”.

<Preparation of B layer>
"B layer-A"
After using NOVAPEX (registered trademark) (polyethylene terephthalate, IV: 0.65, ΔHm = 55 J / g) manufactured by Mitsubishi Chemical Corporation as the polyester resin, NOVAPEX was first kneaded at 260 ° C. with a 40 mm diameter single screw extruder. Then, it was extruded from the die, and then rapidly cooled with a casting roll at about 40 ° C. to produce an amorphous sheet having a thickness of 225 μm. Next, the paper is passed through a sequential biaxial tenter manufactured by Mitsubishi Heavy Industries, Ltd., stretched at 95 ° C. in the MD (longitudinal direction) at a stretch ratio of 3 times, and subsequently at 110 ° C. in the TD (transverse direction) at the stretch ratio. The film was stretched 3 times. Thereafter, a heat treatment was performed at 160 ° C. for 15 seconds to obtain a biaxially stretched film having a thickness of 25 μm.

"B layer-B"
An amorphous sheet having a thickness of 108 μm 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 μm.

"B layer-C"
As polyester-based resin, Eastman Chemical Co., Ltd., copyester 6763 (polyethylene terephthalate glycol, glass transition temperature = 81 ° C., ΔHm = 0 J / g) was used. Then, it was quenched with a casting roll at about 40 ° C. to produce an amorphous sheet having a thickness of 25 μm.

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 ΔHm: 22.8 J / g), as a flame retardant, fine particle size melamine (average particle size 5 μm) 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. using a 40 mm diameter co-axial twin screw extruder, extruded from a T die, and simultaneously layer B-A is bonded from the cast roll side. As a result, a laminated body (A layer = 25 μm, B layer−A = 25 μm) having a layer configuration of A layer / B layer was obtained. Table 3 shows the results of evaluation of flame retardancy, peel strength, tensile strength, and tensile elongation of the obtained laminate.

(Example 3-2)
As the A layer, a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm) was obtained in the same manner as in Example 3-1, except that the mixing mass ratio of Byron GM-443 and fine particle size melamine was 60:40. ) Was obtained. Table 3 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Example 3-3)
As the A layer, a thickness of 50 μm (A layer = 25 μm, B layer−A layer = with the same method as in Example 3-1 except that the mixing mass ratio of Byron GM-443 and fine particle size melamine was 40:60. 25 μm) was obtained. Table 3 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Example 3-4)
As the A layer, a thickness of 50 μm (A layer = 25 μm, B layer−A layer = the same as in Example 3-1) except that the mixing mass ratio of Byron GM-443 and fine particle size melamine was 25:75. 25 μm) was obtained. Table 3 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Example 3-5)
Byron GM-443 and fine particle size 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 Are laminated from the cast roll side and the nip roll side to form a laminate having a layer configuration of B layer-A / A layer / B layer-A with a thickness of 70 μm (A layer = 20 μm, B layer-A = 25 μm). Obtained. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.

(Example 3-6)
A laminate having a thickness of 40 μm (A layer = 28 μm, B layer−B = 12 μm) 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 3-7)
Byron GA-1300 manufactured by Toyobo Co., Ltd. (terephthalic acid: 32.8 mol%, isophthalic acid: 5.1 mol%, adipic acid: 12.1 mol%, 1,4-butanediol: 50 mol% as the polyester resin (A) And a glass transition temperature = −6 ° C., ΔHm = 23.7 J / g), and a thickness of 50 μm (A layer = 25 μm, B layer—A = 25 μm) in the same manner as in Example 3-2 Got the body. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.

(Example 3-8)
Byron 30P manufactured by Toyobo Co., Ltd. (terephthalic acid: 27.0 mol%, isophthalic acid: 23.0 mol%, ethylene glycol: 50 mol%, glass transition temperature = −28 ° C., ΔHm = 9.0 J / G) was used to obtain a laminate having a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm) in the same manner as in Example 3-2. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.

(Example 3-9)
By mixing Byron GM-443, Byron 30P, and fine particle size melamine at a mass ratio of 20:40:40 as the A layer, the thickness was 50 μm (A layer = 25 μm, A laminate of (B layer−A layer = 25 μm) was obtained. Table 3 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Example 3-10)
Example 3-2 except that GSPla AD92W (polybutylene succinate-adipate copolymer, glass transition temperature = −40 ° C., ΔHm = 35 J / g) manufactured by Mitsubishi Chemical Corporation was used as the polyester resin (A). A laminate having a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm) was obtained in the same manner. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.

(Example 3-11)
Example 3-2 except that BASF Ecoflex F (polybutylene adipate-terephthalate copolymer, glass transition temperature = −30 ° C., ΔHm = 21 J / g) was used as the polyester resin (A). In this way, a laminate having a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm) was obtained. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.

(Example 3-12)
As the polyester-based resin (A), GSPla AD92W (polybutylene succinate-adipate copolymer, ΔHm = 35 J / g) manufactured by Mitsubishi Chemical Corporation was used in the same manner as in Example 3-1. By the method, a laminate having a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm) was obtained. 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 μm 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. By laminating from the nip roll side and the nip roll side, a laminate having a layer structure of B layer-A / A layer / B layer-A having a thickness of 100 μm was obtained. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.

(Example 3-15)
A laminate having a thickness of 50 μm 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 3-16)
A laminate having a thickness of 50 μm (A layer = 25 μm, B layer-C = 25 μm) was obtained in the same manner as in Example 3-2 except that B layer-C was used instead of B layer-A. Table 3 shows the results of evaluation similar to that of Example 3-1 for the obtained laminate.

(Example 3-17)
A laminate having a thickness of 50 μm 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.

(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 μm 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.

(Comparative Example 3-2)
As the A layer, a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm) was obtained in the same manner as in Example 3-1, except that the mixing mass ratio of Byron GM-443 and fine particle size melamine was 95: 5. ) Was obtained. Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Comparative Example 3-3)
IUPEC made by Mitsubishi Gas Chemical Company instead of polyester resin (A)
PEC-350 (polybutylene succinate-carbonate copolymer, ΔHm = 55 J / g) was used and dry blended at a mixing mass ratio of IUPEC PEC-350 and fine particle size melamine of 60:40. 1 to obtain a laminate having a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm). Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Comparative Example 3-4)
MC-600 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. was used in place of the fine particle size melamine, and Byron GM-443 and MC-601 were blended at a mixing mass ratio of 60:40, and then the same as in Example 3-1. In this way, a laminate having a thickness of 50 μm (A layer = 25 μm, B layer−A = 25 μm) was obtained. Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Comparative Example 3-5)
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. A laminated body of 50 μm (A layer = 25 μm, B layer−A = 25 μm) was obtained. Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Comparative 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 μm 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.

(Comparative Example 3-7)
A layer having a thickness of 50 μm (A layer = 25 μm, B layer—A = 25 μm) was prepared in the same manner as in Example 3-1, except that the mixing mass ratio of GSPla AD92W and fine particle size melamine was 95: 5. A laminate was obtained. Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Comparative 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 μm laminate was obtained. Table 4 shows the results of evaluation similar to Example 3-1 for the obtained laminate.

(Comparative Example 3-9)
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 μm 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.

From Table 3, the flame retardancy of the third flame retardant laminates of Examples 3-1 to 17 passes UL94VTM and is good with less combustion time. In addition, 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. Although 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. .

On the other hand, 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. In 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. In Comparative Example 3-3, the polyester resin (A) has a heat of crystal fusion ΔHm 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. Since 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. In 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. Since Comparative Example 3-8 uses melamine cyanurate, the flame retardancy is inferior to that of the third flame retardant laminate. Since Comparative Example 3-9 uses aluminum hydroxide instead of melamine, the flame retardancy is inferior to that of the third flame retardant laminate.

As described above, 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.

[Example and Comparative Example of Fourth Embodiment]
Next, examples and comparative examples according to the fourth embodiment will be described.
The results shown in the examples were evaluated by the following methods.

(1) Flame retardancy Measurement and evaluation were performed in the same manner as in the example according to the third embodiment.

(2) Adhesiveness with metal As an adhesive evaluation with a metal, the peel strength between the A layer and the tin-plated copper foil was measured by the method shown in FIG.
The peel strength was measured using a tensile tester (manufactured by Intesco Corporation: material tester with thermostat 201X). An evaluation sample having a width of 10 mm was used, and a 180 ° C. peeling test was performed at an atmospheric temperature of −20 ° C., 23 ° C. and 80 ° C., and a peeling speed of 10 mm / min. A film having a peel strength of 5 N / 10 mm (that is, 5 N / cm) or more at all temperatures was accepted.

(3) Heat resistance A sample for evaluation (flat cable) having a length of 600 mm × width of 30 mm (thickness varies depending on each test piece) is left in a baking test apparatus (DKS-5S manufactured by Daiei Kagaku Seiki Seisakusho). And heated at 120 ° C. for 24 hours.
Visually observe the appearance of the sample after heating, “○” if there is no copper foil peeling, flat cable shrinkage, wrinkles, deformation, etc., copper foil peeling, flat cable shrinkage, wrinkles, deformation, etc. What was produced was evaluated as “x”.

<Preparation of layer B>
The following two types of films (“B layer-A” and “B layer-B”) were prepared and prepared as the film constituting the B layer.

“B layer-A”:
Using Novapex (polyethylene terephthalate, glass transition temperature = 79 ° C., ΔHm = 55 J / g) manufactured by Mitsubishi Chemical Corporation as the polyester-based resin, the Novapex was first kneaded at 260 ° C. with a 40 mmφ single screw extruder and then extruded from the die. Then, it was rapidly cooled with a casting roll at about 40 ° C. to produce an amorphous sheet having a thickness of 225 μm. Next, the paper is passed through a sequential biaxial tenter manufactured by Mitsubishi Heavy Industries, Ltd., stretched at 95 ° C. in the MD (longitudinal direction) at a stretch ratio of 3 times, and subsequently at 110 ° C. in the TD (transverse direction) at the stretch ratio. The film was stretched 3 times. Thereafter, a heat treatment was performed at 160 ° C. for 15 seconds to obtain a biaxially stretched film having a thickness of 25 μm.

“B layer-B”:
A polyesterester 6663 manufactured by Eastman Chemical Co. (polyethylene terephthalate glycol, glass transition temperature = 81 ° C., ΔHm = 0 J / g) was used, and the coupler 6663 was kneaded at 260 ° C. with a 40 mmφ single screw extruder and then extruded from the die. Then, it was quenched with a casting roll at about 40 ° C. to produce an amorphous sheet having a thickness of 25 μm.

Example 4-1
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 fusion ΔHm: 22.8 J / g), melamine (average particle size: 5 μm) manufactured by Nissan Chemical Co., Ltd. as a flame retardant, and E4275 manufactured by Japan Epoxy Resin Co., Ltd. as a phenoxy resin. (Bisphenol F / bisphenol A = 75 mol%, 25 mol%) was used.
These Byron GM-443, melamine, and E4275 were dry blended at a mixing mass ratio of 58/40/2, and then kneaded at 190 ° C. using a 40 mmφ co-directional twin-screw extruder, and a single die attached with a T-die. It is melted again with a shaft extruder, extruded into a sheet form from a die, extruded from a T die, and at the same time, “B layer-A” is bonded from the cast roll side, so that the layer structure becomes A layer / B layer. A laminated film with a thickness of 65 μm (A layer = 40 μm, B layer−A = 25 μm) was obtained.
The obtained laminated film was tested for flame retardancy, and the results are shown in Table 5.

Next, a tin-plated copper foil having a thickness of 150 μm 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.

In addition, regarding any one of the flame retardant properties, heat resistance, and adhesion between the A layer and the tin-plated copper foil, 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 4-2)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was 55: 40: 5. A laminated film of A = 40 μm) 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.

(Example 4-3)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was set to 50:40:10. A laminated film of A = 40 μm) 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.

(Example 4-4)
Byron GA-1300 manufactured by Toyobo Co., Ltd. (terephthalic acid: 32.8 mol%, isophthalic acid: 5.1 mol%, adipic acid: 12.1 mol%, 1,4-butanediol: 50 mol% as the polyester resin (A) Glass transition temperature = −6 ° C., ΔHm = 23.7 J / g), and the mixing mass ratio of Byron GA-1300, melamine and E4275 was set to 50:40:10, and the same as Example 4-1. A laminated film having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained by this method.
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.

(Example 4-5)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-4 except that the mixing mass ratio of Byron GA-1300, melamine and E4275 was set to 40:40:20. A laminated film of A = 40 μm) 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.

(Example 4-6)
As the polyester resin (A), Byron 30P manufactured by Toyobo Co., Ltd. (terephthalic acid: 27.0 mol%, sebacic acid: 23.0 mol%, ethylene glycol: 50 mol%, glass transition temperature = −28 ° C., ΔHm = 9.0 J / G) and a thickness of 65 μm (A layer = 25 μm, B layer−A =) by the same method as in Example 4-1, except that the mixing mass ratio of Byron 30P, melamine and E4275 was 50:40:10. 40 μm) laminated film 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.

(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 having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as in Example 4-1, except that
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.

(Example 4-8)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was set to 65: 30: 5. A laminated film of A = 40 μm) 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.

(Example 4-9)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was set to 35: 60: 5. A laminated film of A = 40 μm) 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.

(Example 4-10)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was 78: 20: 2. A laminated film of A = 40 μm) 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.

(Example 4-11)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was 28: 70: 2. A laminated film of A = 40 μm) 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.

(Example 4-12)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was 18: 80: 2. A laminated film of A = 40 μm) 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.

(Example 4-13)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was set to 35:40:25. A laminated film of A = 40 μm) 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.

(Example 4-14)
As the A layer, a thickness of 65 μm (A layer = 25 μm, B layer—A =) was obtained in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was set to 30:40:30. 40 μm) laminated film 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.

(Example 4-15)
Example 1 except that E1256 (bisphenol A = 100 mol%) manufactured by Japan Epoxy Resin Co., Ltd. was used as the phenoxy resin, and the mixing mass ratio of Byron GM-443, melamine and E1256 was 55: 40: 5 in the configuration of layer A A laminated film having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as in 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 6.

(Example 4-16)
As the polyester resin (A), GSPla AZ91T (polybutylene succinate, glass transition temperature: −30 ° C., ΔHm: 54.0 J / g) manufactured by Mitsubishi Chemical Corporation was used. In the configuration of the A layer, GSPla AZ91T, melamine and A laminated film having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as in Example 4-1, except that the mixing mass ratio of E4275 was 55: 40: 5.
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.

(Comparative Example 4-1)
In the structure of the A layer, after blending Byron GM-443 and melamine at a mixing mass ratio of 60:40 without using a phenoxy resin, the thickness was 65 μm (A layer = 25 μm, A laminated film of B layer-A = 40 μm 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.

(Comparative Example 4-2)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was 90: 5: 5. A laminated film of A = 40 μm) 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.

(Comparative Example 4-3)
In the configuration of layer A, MC-600 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. was used instead of melamine, and Byron GM-443, MC-601 and E4275 were blended at a mixing mass ratio of 55: 40: 5, A laminated film having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as in 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.

(Comparative Example 4-4)
In the configuration of the A layer, BF013ST (aluminum hydroxide) manufactured by Nippon Light Metal Co., Ltd. was used instead of melamine, and Byron GM-443, BF013ST and E4275 were blended at a mixing mass ratio of 55: 40: 5, and then Example 4-1 A laminated film having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as above.
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.

(Comparative Example 4-5)
A thickness of 65 μm (A layer = 40 μm, B layer) in the same manner as in Example 4-2, except that “B layer-B” was used instead of “B layer-A” as the film constituting the B layer. -C = 25 μm) 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.

(Comparative Example 4-6)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was set to 60: 39.5: 0.5. , B layer-A = 40 μm).
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.

(Comparative Example 4-7)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was set to 25:40:35. A laminated film of A = 40 μm) 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.

(Comparative Example 4-8)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was 83: 15: 2. A laminated film of A = 40 μm) 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.

(Comparative Example 4-9)
As the A layer, a thickness of 65 μm (A layer = 25 μm, B layer−A =) was obtained in the same manner as in Example 4-1, except that the mixing mass ratio of Byron GM-443, melamine and E4275 was 13: 85: 2. 40 μm) laminated film 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.

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.
Further, when Comparative Example 4-3 using melamine cyanurate other than melamine was compared with Examples, it was found that flame retardancy can be remarkably increased by using melamine. 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 retardancy of the laminated film can be significantly increased.
In the above test, the adhesion with copper-plated tin was examined. However, the adhesion between the phenoxy resin and the metal is considered to be due to the hydrogen bond between the moisture present on the metal surface and the phenoxy resin. It is considered that the same adhesiveness can be obtained for other metals (for example, silver, gold, platinum, iron, stainless steel, steel or alloys thereof).

Compared to Example 4-1, Examples 4-4 to 7 use polyester resins (A) having different glass transition temperatures and ΔHm. Considering these results and previous experience, the polyester resin (A) has higher peel strength at lower temperatures (for example, 0 ° C. or lower) when Tg is lower, and crystallinity when ΔHm is higher. It was found that the heat resistance tends to be high because of the high value.
From this viewpoint, 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. or lower.
Further, the heat of crystal fusion ΔHm 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.

On the other hand, regarding the polyester-based resin (B), when considering the evaluation results of the above-mentioned Examples and Comparative Examples, particularly the evaluation results of Comparative Example 4-5 and the experience so far, the glass of the polyester-based resin (B) The transition temperature is preferably 50 to 120 ° C., the lower limit is particularly preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and the upper limit is particularly 110 ° C. or lower, especially 100 ° C. or lower. It can be considered more preferable.
The crystal melting heat ΔHm 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.

From the results of the above Examples and Comparative Examples and the experience so far, 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%.

In addition, comparing Example 4-15 with other examples and taking into account previous experience, the reason is not clear, but among bisphenols, bisphenol F is more flame retardant than bisphenol A. It turned out to be excellent.

[Example and Comparative Example of Fifth Embodiment]
Next, examples and comparative examples according to the fifth embodiment will be described.

(2) Tensile strength and tensile elongation Measurement and evaluation were performed in the same manner as in the example according to the third embodiment.

(3) Heat resistance (softening temperature)
Using a sample for evaluation of 5 mm length × 5 mm width (thickness varies depending on each test piece), the softening temperature was measured by TMA based on JIS K7196. Measure the TMA curve at an ambient temperature of 23 ° C, a relative humidity of 50%, an indenter pressure of 0.5N, and a heating rate of 5 ° C / min. The intersection point with the extension of the tangent of the portion where the penetration speed is maximum to the low temperature side was defined as the needle penetration temperature, and the softening temperature was calculated from this value. The softening temperature passed 140 ° C. or higher.

<Preparation of B layer>
"B layer-1"
As a polyester resin, Novapex (polyethylene terephthalate, glass transition temperature = 79 ° C., ΔHm = 55 J / g) manufactured by Mitsubishi Chemical Corporation was used. First, Novapex was kneaded at 260 ° C. with a 40 mm diameter single screw extruder, and then from the die. Extrusion was followed by quenching with a casting roll at about 40 ° C. to produce an amorphous sheet having a thickness of 225 μm. Next, the paper is passed through a sequential biaxial tenter manufactured by Mitsubishi Heavy Industries, Ltd., stretched at 95 ° C. in the MD (longitudinal direction) at a stretch ratio of 3 times, and subsequently at 110 ° C. in the TD (transverse direction) at the stretch ratio. The film was stretched 3 times. Thereafter, a heat treatment was performed at 160 ° C. for 15 seconds to obtain a biaxially stretched film having a thickness of 25 μm.

"B layer-2"
An amorphous sheet having a thickness of 108 μm 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 μm. It was.

"B layer-3"
A 25 μm-thick biaxial film in the same manner as “B layer-1” except that NW4032D (polylactic acid, glass transition temperature = 55 ° C., ΔHm = 42 J / g) manufactured by Nature Works is used as the polyester resin. A stretched film was obtained.

Example 5-1
As the A layer, GSPla AZ91T (polybutylene succinate, glass transition temperature = −30 ° C., ΔHm = 54.0 J / g) manufactured by Mitsubishi Chemical Corporation, fine powdered melamine (melamine) manufactured by Nissan Chemical Industries, and TMAIC manufactured by Nippon Kasei Co., Ltd. ( GSPla AZ91T, fine melamine, and TMAIC were dry blended at a mixing mass ratio of 69: 30: 1 using a mixture of trimethallyl isocyanate, and then kneaded at 190 ° C. using a 40 mm diameter co-directional twin screw extruder. Then, a sheet (A layer) having a thickness of 50 μm was obtained with a casting roll at 55 ° C. Next, as both outer layers of the A layer, 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 μm. . Subsequently, the laminate was irradiated with radiation (γ 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 μm. 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 μm. 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 μm 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 μm, and layer B-2 was used as layer B. The body was prepared and evaluated. The results are shown in Table 8.

(Example 5-10)
GSPla AD92W (polybutylene succinate / adipate copolymer, glass transition temperature = −40 ° C., ΔHm = 35 J / g) manufactured by Mitsubishi Chemical Corporation as polyester resin (A) is mixed with GSPla AD92W, fine melamine and TMAIC After dry blending at a mass ratio of 59: 40: 1, a laminate was produced and evaluated in the same manner as in Example 5-1. 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 μm. 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.

(Comparative 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.

(Comparative 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 μm. The results are shown in Table 8.

(Comparative Example 5-3)
Table 8 shows the results of preparation and evaluation of the laminate in Example 5-2 without adding a crosslinking agent.

(Comparative 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.

(Comparative 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 μm. The results are shown in Table 8.

(Comparative 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.

(Comparative 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.

(Comparative Example 5-8)
As layer A, Toyobo Co., Ltd. Byron (registered trademark) GA1310 (polyester copolymer (35 mol% terephthalic acid, 15 mol% isophthalic acid, 50 mol% 1,4-butanediol), glass transition temperature = 27 ° C, ΔHm = 26.1 J / g), and a laminate was prepared and evaluated in the same manner as in Example 5-3 except that the mixing mass ratio of GA1310, fine melamine, and TMAIC was 49: 50: 1. The results are shown in Table 8.

(Comparative 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.

From Table 8, the flame retardancy of the laminates of Examples 5-1 to 12 passed UL94VTM, the combustion time is good, the heat resistance is good, and the mechanical strength is sufficient. The overall evaluation was ○.

On the other hand, 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. In 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. In 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.

As described above, 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. In addition, 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.

[Example and Comparative Example of Sixth Embodiment]
Next, examples and comparative examples according to the sixth embodiment will be described.

(1) Flame retardancy (UL94VTM) (laminate)
Combustion was performed 5 times based on the safety standard UL94 vertical combustion test procedure of Underwriters Laboratories using an evaluation sample (laminate) of length 200 mm x width 50 mm (thickness varies depending on each specimen). The test was conducted.
Based on the criteria of UL94 vertical combustion test UL94VTM, those satisfying the VTM-0 standard were marked with ◯, and those not satisfying were marked with x.

(2) Flame resistance (UL1581VW-1) (flat cable)
A sample for evaluation (flat cable) measuring 600 mm long × 19 mm wide (thickness varies depending on each test piece) is ignited for 15 seconds using a tyryl burner and 5 seconds rest for 15 seconds based on the UL 1581VW-1 standard combustion test method. The determination was made by repeating the test times, the burning time of the test piece, the damage ratio of the indicator, and whether or not the absorbent cotton was ignited by drip. UL1581VW-1 passed when the burning time was 60 seconds or less, the indicator damage rate was 25% or less, and the absorbent cotton was not ignited by drip. In Table 9, “Obtained” was marked with “OK”, and “X” was rejected.

(4) Bendability The appearance when a sample for evaluation (flat cable) having a length of 600 mm x a width of 30 mm (thickness varies depending on each test piece) is bent 180 degrees is visually observed, and a copper foil and an adhesive The case where no peeling or cracking occurred was evaluated as “◯”, and the case where it was generated was evaluated as “X”.

<Preparation of B layer>
The following two types of films (“B layer-A” and “B layer-B”) were prepared and prepared as the film constituting the B layer.

“B layer-A”:
Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation (polyethylene terephthalate, glass transition temperature = 79 ° C., ΔHm = 55 J / g) was used as the polyester-based resin. First, Novapex was kneaded at 260 ° C. with a 40 mm diameter single screw extruder. Then, it extruded from the nozzle | cap | die, and then rapidly cooled with a casting roll at about 40 ° C. to produce an amorphous sheet having a thickness of 225 μm. Next, the paper is passed through a sequential biaxial tenter manufactured by Mitsubishi Heavy Industries, Ltd., stretched at 95 ° C. in the MD (longitudinal direction) at a stretch ratio of 3 times, and subsequently at 110 ° C. in the TD (transverse direction) at the stretch ratio. The film was stretched 3 times. Thereafter, a heat treatment was performed at 160 ° C. for 15 seconds to obtain a biaxially stretched film having a thickness of 25 μm.

“B layer-B”:
Using a polyester 6673 (Esterman Chemical Co., Ltd., polyethylene terephthalate glycol, glass transition temperature = 81 ° C., ΔHm = 0 J / g) as a polyester-based resin, the coupler 6663 was kneaded at 260 ° C. with a 40 mm diameter single screw extruder, and then from the die. Extrusion was followed by quenching with a casting roll at about 40 ° C. to produce an amorphous sheet having a thickness of 25 μm.

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 ΔHm: 24.6 J / g), Nissan Chemical Co., Ltd. fine melamine (average particle size 5 μm) is used as a flame retardant, Sakai Kogyo Co., Ltd. PKHB (phenoxy resin) is used as a carbonization accelerator It was.
These Byron GM-480, melamine and PKHB were dry blended at a mixing mass ratio of 55: 40: 5, then kneaded at 190 ° C. using a 40 mm diameter co-directional twin screw extruder, and attached with a T-die. It is melted again with a single screw extruder, extruded into a sheet form from a die, extruded from a T-die, and at the same time, “B layer-A” is bonded from the cast roll side, so that the layer structure becomes A layer / B layer. A laminate having a thickness of 65 μm (A layer = 40 μm, B layer−A = 25 μm) was obtained.

Next, a tin-plated copper foil having a thickness of 150 μm 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.

In addition, regarding flame retardancy, heat resistance, and bendability, if even one of them fails, the overall evaluation is evaluated as “×”, and if all items are acceptable, the overall evaluation is “○”. evaluated.
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 6-2)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) in the same manner as in Example 6-1 except that the mixing mass ratio of Byron GM-480, melamine and PKHB was 50:40:10. A laminate of A = 40 μm) was obtained. Next, 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.

(Example 6-3)
MC-600 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. was used as a carbonization accelerator, and the mixing mass ratio of Byron GM-480, melamine and MC-600 was set to 40:40:20 in the configuration of layer A Obtained a laminate having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) in the same manner as in Example 6-1. Next, 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.

(Example 6-4)
The same as Example 6-1 except that pentaerythritol manufactured by Junsei Chemical Co., Ltd. was used as the carbonization accelerator, and the mixing mass ratio of Byron GM-480, melamine and pentaerythritol was 40:40:20 in the configuration of layer A. In this way, a laminate having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained. Next, 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.

(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 layered product having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as above. Next, 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.

(Example 6-6)
65 μm thickness (A layer = 25 μm, B layer−A = 40 μm) in the same manner except that the mixing mass ratio of Byron GM-480, melamine and MC-600 was 50:30:20 A laminate was obtained. Next, 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.

(Example 6-7)
A layer having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was formed in the same manner except that the mixing mass ratio of Byron GM-480, melamine and PKHB was set to 35: 60: 5. Got the body. Next, 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.

(Example 6-8)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−) except that the mixing mass ratio of Byron GM-480, melamine, PKHB and MC-600 was set to 35: 40: 5: 20. A laminate of A = 40 μm) was obtained. Next, 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.

(Example 6-9)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer−A) except that the mixing mass ratio of Byron GM-480, melamine, PKHB and pentaerythritol was 45: 40: 5: 10. = 40 μm) was obtained. Next, 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.

(Example 6-10)
As a polyester resin (A), Byron (registered trademark) GM-443 manufactured by Toyobo Co., Ltd. (terephthalic acid: 27 mol%, isophthalic acid: 19 mol%, adipic acid: 4 mol%, 1,4-butanediol: 50 mol%, glass Transition temperature: 26 ° C., heat of crystal fusion ΔHm: 22.8 J / g), and in the configuration of layer A, the mixing mass ratio of Byron GM-443, melamine and MC-600 was 40:40:20 A laminate having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as in Example 6-1. Next, 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.

(Example 6-11)
As the polyester resin (A), Byron (registered trademark) 30P manufactured by Toyobo Co., Ltd. (terephthalic acid: 27 mol%, sebacic acid: 23 mol%, ethylene glycol: 50 mol%, glass transition temperature: −28 ° C., heat of crystal melting ΔHm: A thickness of 65 μm in the same manner as in Example 6-1 except that the mixing mass ratio of Byron 30P, melamine and MC-600 was set to 40:40:20 in the configuration of layer A using 2.0 J / g) A laminate of (A layer = 25 μm, B layer−A = 40 μm) was obtained. Next, 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)
65 μm thickness (A layer = 25 μm, B layer−A = 40 μm) in the same manner except that the mixing mass ratio of Byron GM-480, melamine and MC-600 was set to 70:10:20 A laminate was obtained. Next, 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 6-2)
A layer having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was formed in the same manner except that the mixing mass ratio of Byron GM-480, melamine and PKHB was changed to 5: 90: 5 in the configuration of the A layer. Got the body. Next, 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 6-3)
A laminate having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner except that Byron GM-480 and melamine were blended at a mixing mass ratio of 60:40 in the configuration of the A layer. It was. Next, 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 6-4)
In the configuration of the A layer, the thickness was 65 μm (A layer = 25 μm, B layer) except that the mixing mass ratio of Byron GM-480, melamine and MC-600 (melamine cyanurate) was 40:10:50. A laminate of −A = 40 μm was obtained. Next, 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 6-5)
A thickness of 65 μm (A layer = 40 μm, B layer) in the same manner as in Example 6-3, except that “B layer-B” was used instead of “B layer-A” as the film constituting the B layer. A laminate of −C = 25 μm was obtained. Next, 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 6-6)
NW4032D (polylactic acid, glass transition temperature: 55 ° C., heat of crystal fusion ΔHm: 42.5 J / g) manufactured by NatureWorks is used as the polyester resin (A), and NW4032D, melamine and MC-600 are used in the configuration of the A layer. A laminate having a thickness of 65 μm (A layer = 25 μm, B layer−A = 40 μm) was obtained in the same manner as in Example 6-1 except that the mixing mass ratio was 40:40:20. Next, 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.

From Table 9, the flame retardancy of the laminates of Examples 6-1 to 11 passed UL94VTM and was good with little combustion time. In addition, the flat cables made from the laminates of Examples 6-1 to 11 had a short burning time, passed UL1581VW-1, good heat resistance, and good bendability. Became ○.

On the other hand, 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. In Comparative Example 6-2, since the ratio of melamine added to the laminate was large, the flat cable was poor in bendability. In 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. In 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. In Comparative Example 6-5, although the flame retardance of the laminate was good because ΔHm 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.

As described above, 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. In addition, 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.) produced from the laminate according to the sixth embodiment is Good flame retardancy, heat resistance and bendability.

While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and the antistatic resin molded body and the method of manufacturing the molded body with such changes are also described in the present invention. It should be understood as being included in the technical scope of the invention.

Claims

A flame-retardant polyester resin composition comprising 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,
A flame retardant polyester resin composition, wherein the ratio of melamine in the flame retardant polyester resin composition is 10 to 80% by mass.
A polyester resin having a glass transition temperature Tg of −20 ° C. to 40 ° C. and a crystal melting temperature Tm of 140 ° C. to 190 ° C., and a glass transition temperature Tg of −100 ° C. or more and less than −20 ° C. A flame retardant polyester resin composition containing a mixture of a polyester resin having a temperature Tm of 100 ° C. or more and less than 140 ° C. and melamine,
The ratio of melamine in the flame-retardant polyester resin composition is 20 to 60% by mass, and the mass ratio of the former polyester resin and the latter polyester resin is 90:10 to 30:70. The flame-retardant polyester-based resin composition according to claim 1.
The polyester resin contains 50 to 90 mol% of terephthalic acid as a polyvalent carboxylic acid component, and 70 to 100 mol in total of 1,4-butanediol, ethylene glycol, and diethylene glycol as polyhydric alcohol components. % Flame retardant polyester-based resin composition according to claim 1.
4. The flame retardant polyester resin composition according to claim 1, wherein the flame retardant polyester resin composition contains a phenoxy resin.
A flame retardant polyester resin composition containing a mixture of polyester resin, melamine, and phenoxy resin,
The polyester resin 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 contains as the first feature,
The flame retardant according to claim 4, wherein 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. Polyester resin composition.
The flame retardant polyester resin composition according to claim 1, wherein the flame retardant polyester resin composition contains a carbonization accelerator.
The flame retardant polyester resin composition according to claim 6, wherein the carbonization accelerator is a compound having a hydroxyl group.
The flame retardant polyester resin composition according to claim 7, wherein the carbonization accelerator is melamine cyanurate.
The flame retardant polyester resin composition according to claim 1, wherein the flame retardant polyester resin composition contains a crosslinking agent.
The flame retardant polyester resin composition according to claim 9, wherein the crosslinking agent is trimethallyl isocyanate.
A flame-retardant resin body comprising the flame-retardant polyester resin composition according to any one of claims 1 to 10.
A flame retardant laminate having another resin layer on at least one surface of a resin layer comprising the flame retardant polyester resin composition according to any one of claims 1 to 10.
The glass transition temperature is 50 ° C. or higher and the heat of crystal fusion ΔHm is 40 J / g or higher on at least one surface of the resin layer of the resin layer comprising the resin composition according to claim 1. A flame-retardant resin laminate having another resin layer comprising a resin composition containing a polyester resin.
It has an A layer composed of a resin composition a composed mainly of a mixture of a polyester resin having a glass transition temperature of −80 to 30 ° C., a melamine, and a phenoxy resin, and the glass transition temperature is on the A layer. A resin laminate having a B layer composed of a resin composition b mainly composed of a polyester-based resin having a heat of crystal melting ΔHm of 40 to 100 J / g at 50 to 120 ° C .;
The proportion of melamine in the resin composition a constituting the layer A is 20 to 80% by mass, and the proportion of phenoxy resin in the resin composition a is 1 to 30% by mass. The flame-retardant resin laminate according to claim 12 or 13.
Having a layer A composed of a resin composition a whose main component is a mixture of a polyester-based resin having a glass transition temperature of 30 ° C. or less, a melamine and a carbonization accelerator,
On the A layer, a laminate having a B layer composed of a resin composition b mainly composed of a polyester resin having a glass transition temperature of 50 to 120 ° C. and a crystal melting heat ΔHm of 40 to 100 J / g. Yes,
The ratio of the melamine in the resin composition a constituting the layer A is 20 to 80% by mass, and the ratio of the carbonization accelerator in the resin composition a is 1 to 30% by mass. The flame-retardant resin laminate according to claim 12 or 13.
A flame retardant resin laminate according to claim 14 or 15, wherein the flame retardant resin laminate is for metal bonding.
At least one side of the A layer mainly comprising a mixture of a polyester resin having a glass transition temperature of 20 ° C. or lower, a melamine and a crosslinking agent has a B layer having a polyester resin having a glass transition temperature of 60 ° C. or higher as a main component. A laminate,
The gel fraction of the laminate is 15% by mass or more and 55% by mass or less, and the proportion of melamine in the laminate is 10% by mass or more and 40% by mass or less. The flame-retardant resin laminate described.
A wiring cable using the flame-retardant polyester resin composition according to any one of claims 1 to 10.
A wiring cable using the flame retardant resin sheet according to claim 11 or the flame retardant resin laminate according to any one of claims 12 to 17.