KR101165652B1 - Flame-retardant polyester resin composition and flame-retardant laminate - Google Patents

Abstract

The present invention provides a flame-retardant laminate and a flexible flat cable which do not contain a halogen-based compound and the like and which are excellent in flame retardancy, mechanical properties, and surface properties. To this end, the present invention has a glass transition temperature of 30 ° C. or less and a crystal melting amount (ΔHm) of 40 J / g or less on at least one surface of an A layer containing a mixture of melamine and a polyester-based resin (A). It is a laminated body which has B layer, and the content of melamine in the total mass of A layer is 10-80 mass%, The flame-retardant laminated body characterized by the above-mentioned, and the flexible flat cable containing this flame-retardant laminated body are proposed.

Description

Flame-retardant polyester resin composition and flame-retardant laminate {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, heat resistance, specifically, for example, flexible flat cable, electrical insulation, membrane switch circuit printing substrate, copier inner member, It relates to a flame-retardant polyester resin composition and a flame-retardant laminate which can be preferably used in a planar heating element base, an FPC (flexible printed circuit) reinforcement plate, and the like.

Polyester-based resins having excellent insulation properties and flexibility are attracting attention as an alternative to vinyl chloride-based resins. However, polyester-based resins are generally easy to burn, so that flame-retardant is formulated by flame retardant in order to flame-retard these resins. Needs to be.

As flame retardants of polyester resins, halogen flame retardants such as decabromodiphenyl ether and hexabromo diphenyl have been used, but halogen flame retardants are toxic gases such as dioxins generated during combustion. In some cases, it is also a problem in terms of safety during waste incineration and thermal recycling.

Although phosphorus compounds can also be considered, not only are there problems in terms of safety and environmental compatibility, but in particular, when the phosphorus compounds are blended with polyester resins, a decrease in heat resistance due to plasticization and bleeding on the surface of the molded article of the phosphorus compounds are generated. Therefore, it cannot be called a practically preferable technique.

Thus, the present inventors have focused on nitrogen compounds, especially melamine, as non-halogen- and non-phosphorus-based flame retardants used in polyester resins.

Regarding the use of nitrogen-based compounds, particularly melamine, as a flame retardant, for example, Japanese Patent Application Laid-Open No. 54-112958, Japanese Patent Publication No. 60-33850, Japanese Patent Publication No. 59-50184, and Japanese Patent Publication 62-39174 and the like.

On the other hand, as for a flame-retardant laminated body, what is well-known is the laminated | multilayer film which has polyester resin as an inner layer and has a heat resistant resin layer of 50% or more of imidation ratio which consists of polyamic acid in both outer layers is disclosed (Japan Japanese Patent Application Laid-Open No. 2000-280427, Japanese Patent Laid-Open No. 2004-243760).

Moreover, the technique regarding the polyester film which laminated | stacked the resin layer which generate | occur | produces a non-combustible gas on both surfaces of a polyester film is disclosed (Japanese Unexamined-Japanese-Patent No. 2006-35504). However, in the said polyester film, although flame retardance is provided by providing a flame-retardant layer on the surface of a laminated film, since the fall of the mechanical strength represented by tensile strength, impact strength, etc. arises, it is hard to say that it is a practical enough technique. There was a problem.

Since melamine starts decomposition at 220-250 degreeC, there existed a problem that melamine decomposed | disassembled at the shaping | molding temperature of general polyester-type resins, such as PET and PBT, and caused molding defect.

Therefore, in the present invention, by blending melamine as a flame retardant to a specific polyester resin to prepare a flame retardant polyester resin composition, the melamine is not decomposed during molding to cause molding failure, and furthermore, a machine having a polyester resin. It is an object of the present invention to provide a novel flame retardant polyester resin composition capable of maintaining properties and heat resistance.

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 less, a crystal melting temperature (Tm) of 140 ° C. to 190 ° C., and a melamine, and comprising a flame-retardant poly The ratio of the melamine in ester resin composition is 20-60 mass%, The flame-retardant polyester resin composition characterized by the above-mentioned.

The polyester resin whose glass transition temperature (Tg) is 40 degrees C or less and the crystal melting temperature (Tm) is 140 degreeC-190 degreeC has a low melting point compared with general polyester resins, such as PET and PBT, and melamine decomposes. Since molding can be performed at a temperature lower than the temperature to be achieved, it is possible to eliminate the case where melamine decomposes during molding to cause molding failure. Furthermore, excellent flexibility and mechanical properties can be obtained.

By blending melamine with such specific polyester resins, it is possible to obtain an excellent addition of flame retardancy, mechanical properties, and heat resistance, which is lower than the inorganic flame retardants conventionally studied, without impairing the properties of polyester resins. .

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing explaining the measuring method of the peeling strength between A layer and tin-plated copper foil which were performed as evaluation of peeling strength with a tin-plated copper foil in the Example and comparative example of a 4th flame-retardant laminated body. .

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, the scope of the present invention is not limited to embodiment described below.

[First Embodiment]

The flame-retardant polyester-based resin composition (hereinafter referred to as "first flame-retardant resin composition") according to the first embodiment 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 a flame retardant poly further containing a polyester resin (1-B). Ester resin composition.

(Polyester Resin (1-A))

Polyester-based resin (1-A) is polyester-based resin which is a polycondensation polymer of polyhydric carboxylic acid and a polyhydric alcohol.

As a specific example of polyhydric carboxylic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid, etc. are mentioned, for example.

As a specific example of polyhydric alcohol, ethylene glycol, propylene glycol, 1, 4- butanediol, 1, 6- hexanediol, cyclohexanediol, polyoxyene glycol, polytetramethylene ether glycol, etc. are mentioned, for example.

Especially, it is preferable that it is a copolymer which consists of at least 1 sort (s) of polyhydric carboxylic acid component chosen from terephthalic acid, isophthalic acid, and adipic acid, and at least 1 sort (s) of polyhydric alcohol component chosen from 1, 4- butanediol and ethylene glycol. .

In polyester-based resin (1-A), it is preferable that the ratio of terephthalic acid to a polyhydric carboxylic acid component is 50-90 mol%. The polyester resin (1-A) having such a composition has a lower melting point than ordinary polyester resins such as PET and PBT, and can be molded at a temperature lower than the temperature at which melamine starts decomposition. This can eliminate the case of decomposition and causing molding failure. Furthermore, excellent flexibility and mechanical properties can be obtained.

From such a viewpoint, it is more preferable that polyester resin (1-A) contains terephthalic acid 55 mol% or more, especially 60 mol% or more as a polyhydric carboxylic acid component, Furthermore, 85 mol% or less, Especially 80 mol% It is more preferable to contain below.

However, it is not the intention to limit to the polyester resin whose ratio of terephthalic acid in a polyhydric carboxylic acid component is 50-90 mol%.

In polyester-type resin (1-A), it is preferable that the total ratio of 1, 4- butanediol and ethylene glycol in a polyhydric alcohol component contains 70-100 mol%. If it is polyester-type resin (1-A) which has such a composition, the outstanding flexibility, a mechanical characteristic, and also heat resistance can be obtained.

From such a viewpoint, it is preferable that polyester resin (1-A) contains 1, 4- butanediol and ethylene glycol in total as 75 mol% or more, especially 80 mol% or more as a polyhydric alcohol component, and contains 100 mol% More preferably.

However, as a polyhydric alcohol component, any 1 type of 1, 4- butanediol, ethylene glycol, and diethylene glycol may be contained, and 2 or more types may be contained.

It is preferable that glass transition temperature (Tg) of polyester-type resin (1-A) is 40 degrees C or less, especially -20-40 degreeC. If Tg of polyester-type resin (1-A) is such a temperature range, a flame-retardant polyester-based resin composition excellent in mechanical characteristics, such as flexibility and tensile strength, can be prepared. From this viewpoint, Tg of polyester-based resin (1-A) is especially -15 degreeC or more, especially -10 degreeC or more, and it is especially preferable that it is 35 degrees C or less, especially 30 degrees C or less.

It is preferable that the crystal melting temperature (Tm) of polyester-type resin (1-A) is 140-190 degreeC. If the crystal melting temperature (Tm) of polyester resin (1-A) is such a range, a flame-retardant polyester resin composition excellent in mechanical characteristics, such as flexibility and tensile strength, can be prepared. In view of this, the Tm of the polyester resin (1-A) is particularly preferably 145 ° C or higher, particularly 150 ° C or higher, and particularly preferably 185 ° C or lower, particularly 180 ° C or lower.

It is preferable that the crystal melting heat amount ((DELTA) Hm) of polyester-type resin (1-A) is 20-40 J / g. If (DELTA) Hm of polyester-type resin (1-A) is such a range, a flame-retardant polyester-based resin composition excellent in mechanical characteristics, such as flexibility and tensile strength, can be prepared. From this viewpoint, it is preferable that (DELTA) Hm of polyester-type resin (1-A) is especially 22 J / g or more, especially 25 J / g or more, Furthermore, especially 38 J / g or less, especially 35 J / g It is preferable that it is the following.

It is preferable that the mass mean molecular weights of polyester-type resin (1-A) are 10,000-300,000. If the mass average molecular weight of the polyester-based resin (1-A) is within this range, flexibility can be obtained, and furthermore, since the melt viscosity is appropriate, there is a low possibility of problems in molding processing.

From this point of view, the mass average molecular weight of the polyester resin (1-A) is particularly preferably 20,000 or more, particularly 30,000 or more, and particularly preferably 200,000 or less, particularly 150,000 or less.

In addition, a mass average molecular weight can be measured by the following method. The same applies to other resins.

Using gel permeation chromatography, solvent chloroform, solution concentration 0.2 wt / vol%, solution injection amount 200 μl, solvent flow rate 1.0 mL / min, solvent temperature 40 ° C. were measured, and the mass average molecular weight could be calculated in polystyrene conversion. have. The mass average molecular weight of the standard polystyrene used at this time is 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, 600.

(Polyester Resin (1-B))

Polyester resin (1-B) is polyester resin which is a polycondensation polymer of polyhydric carboxylic acid and a polyhydric alcohol.

As a specific example of polyhydric carboxylic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid, etc. are mentioned, for example.

As a specific example of polyhydric alcohol, ethylene glycol, propylene glycol, 1, 4- butanediol, 1, 6- hexanediol, cyclohexanediol, polyoxyene glycol, polytetramethylene ether glycol, etc. are mentioned, for example.

Especially, it is preferable that it is a copolymer which consists of at least 1 sort (s) of polyhydric carboxylic acid component chosen from terephthalic acid, isophthalic acid, and adipic acid, and at least 1 sort (s) of polyhydric alcohol component chosen from 1, 4- butanediol and ethylene glycol. .

In polyester-based resin (1-B), it is preferable that the ratio of terephthalic acid to a polyhydric carboxylic acid component is 20 mol% or more and less than 70 mol%.

When the polyester-based resin (1-B) having such a composition is blended together with the polyester-based resin (1-A), flexibility, particularly excellent elongation can be obtained, which is preferable. From such a viewpoint, it is more preferable that polyester resin (1-B) contains 30 mol% or more, especially 40 mol% or more of terephthalic acid as a polyhydric carboxylic acid component, Furthermore, it is less than 65 mol%, especially 60 mol It is more preferable to contain less than%.

However, the content of the terephthalic acid in the polyvalent carboxylic acid component is not limited to the polyester resin having 20 mol% or more and less than 70 mol%.

In polyester-based resin (1-B), it is preferable that the total ratio of 1, 4- butanediol and ethylene glycol in a polyhydric alcohol component is 65-100 mol%. When the polyester-based resin (1-B) having such a composition is blended with the polyester-based resin (1-A), mechanical properties can be further improved without inhibiting the heat resistance of the polyester-based resin (1-A). Can be.

From such a viewpoint, it is preferable that polyester resin (1-B) contains 1, 4- butanediol and ethylene glycol as a polyhydric alcohol component in total 70 mol% or more, especially 75 mol% or more, and it is especially 95 It is more preferable to contain 90 mol% or less, especially 90 mol% or less.

However, as a polyhydric alcohol component, any 1 type of 1, 4- butanediol, ethylene glycol, and diethylene glycol may be contained, and 2 or more types may be contained.

It is preferable that the glass transition temperature (Tg) of polyester-type resin (1-B) is -100 or more and less than -20 degreeC. When Tg of polyester-type resin (1-B) is such a temperature range, by mix | blending with the said polyester-type resin (1-A), flexibility, especially elongation can be raised, and the effect is thin with a thickness of 200 micrometers or less. It is especially effective in a film. From such a viewpoint, it is preferable that polyester resin (1-B) is -90 degreeC or more, especially -80 degreeC or more, and it is preferable that it is less than -25 degreeC and especially -30 degreeC.

It is preferable that the crystal melting temperature (Tm) of polyester-type resin (1-B) is 100 degreeC or more and less than 140 degreeC. If the crystal melting temperature (Tm) of polyester resin (1-B) is such a range, a flame-retardant polyester resin composition excellent in mechanical characteristics, such as flexibility and tensile strength, can be prepared. From this viewpoint, it is preferable that especially Tm of polyester-type resin (1-B) is 105 degreeC or more, especially 110 degreeC or more, and also it is especially less than 135 degreeC, and especially it is less than 130 degreeC.

It is preferable that crystal melting amount ((DELTA) Hm) of polyester-type resin (1-B) is 1 J / g or more and less than 20 J / g. If (DELTA) Hm of polyester-type resin (1-B) is such a range, the mechanical characteristics, especially elongation and flexibility of a flame-retardant polyester-type resin composition can be improved further. From this viewpoint, it is preferable that (DELTA) Hm of polyester-type resin (1-B) is especially 5 J / g or more, especially 10 J / g or more, Furthermore, it is especially less than 18 J / g, especially 15 J / g It is preferable that it is less than.

It is preferable that the mass mean molecular weights of polyester-type resin (1-B) are 10,000-300,000. If the mass average molecular weight of the polyester resin (1-B) is within this range, flexibility can be obtained, and furthermore, since the melt viscosity is appropriate, there is a low possibility of problems in molding processing.

From this point of view, the mass average molecular weight of the polyester resin (1-B) is particularly preferably 20,000 or more, particularly 30,000 or more, and particularly preferably 200,000 or less, particularly 150,000 or less.

In addition, a mass average molecular weight can be measured by the following method. The same applies to other resins.

Using gel permeation chromatography, solvent chloroform, solution concentration 0.2 wt / vol%, solution injection amount 200 μl, solvent flow rate 1.0 mL / min, solvent temperature 40 ° C. were measured, and the mass average molecular weight could be calculated in polystyrene conversion. have. The mass average molecular weight of the standard polystyrene used at this time is 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, 600.

(Melamine)

Melamine is a kind of organic nitrogen compound which has a triazine ring in the center of a structure, for example, 2,4,6-triamino-1,3,5-triazine is mentioned. Since melamine generates incombustible gas at the time of combustion, it can flame-retard the 1st flame-retardant resin composition.

Melamine is generally difficult to be used as a flame retardant because its decomposition initiation temperature is lower than that of melamine derivatives (for example, melamine cyanurate, melamine phosphate, etc.) and also has no carbonization promoting action. By blending into polyester-based resin (1-A) or polyester-based resin (1-A) and (1-B), melt kneading can be carried out at or below the decomposition start temperature of melamine, and decomposition of the resin at the time of combustion. Since melamine is decomposed earlier, excellent flame retardancy can be imparted by the endothermic action during sublimation and the generation of an inert gas.

The average particle diameter of melamine is 10 micrometers or less, It is preferable that it is 0.5 micrometer-10 micrometers especially. If the average particle diameter of melamine is in this range, since melamine is not secondary aggregated and is uniformly dispersed in a resin composition, flame retardance can be improved without impairing the mechanical strength of a 1st flame-retardant resin composition. From this point of view, the average particle diameter of melamine is particularly preferably 1.0 µm or more, particularly 1.5 µm or more, and particularly preferably 8.0 µm or less, particularly 6.0 µm or less.

In addition, the said average particle diameter is the value which computed melamine as a circle equivalent diameter.

Melamine can be surface-treated in the range which does not impair the effect of this invention.

As a specific example of surface treatment, surface treatment using silane coupling agents, titanate coupling agents, higher fatty acids, etc., such as epoxy silane, vinyl silane, methacryl silane, amino silane, and isocyanate silane, is mentioned.

By treating melamine with these surface treating agents, the dispersibility of melamine can be improved and the flame retardance of the first flame retardant resin composition can be further improved.

Moreover, you may use together melamine and another flame retardant thru | or a flame retardant adjuvant in the range which does not impair the effect of this invention.

Specific examples of other flame retardants include, for example, phosphorus compounds such as phosphate esters, phosphate esteramides, condensed phosphate esters, phosphazene compounds and polyphosphates, aluminum hydroxide, magnesium hydroxide, calcium aluminate hydrates and tin oxide hydrates. And metal hydroxides.

As a specific example of a flame retardant adjuvant, For example, Metal compounds, such as zinc stannate, zinc borate, iron nitrate, copper nitrate, and a sulfonate metal salt, silicone compounds, such as dimethyl silicone, phenyl silicone, and fluorine silicon, polytetrafluoroethylene, etc. A fluorine compound is mentioned.

By using these flame retardants and a flame retardant adjuvant together, the flame retardance of a 1st flame retardant resin composition can be improved further.

(Mixing ratio)

It is preferable that the compounding ratio of melamine which occupies in a 1st flame-retardant resin composition is 20-60 mass%. When 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 the mechanical properties are not impaired when the blending ratio of melamine is 60% by mass or less. 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 particularly preferably 30% by mass or more. Moreover, it is especially preferable that it is 50 mass% or less, and especially it is more preferable that it is 40 mass% or less.

In addition, when mix | blending polyester resin (1-B), the mixing ratio of polyester resin (1-A) and polyester resin (1-B) is 90: 10-30: 70 by mass ratio. Is preferably. If it is such a ratio, a mechanical characteristic can be improved further without impairing the heat resistance which polyester-type resin (1-A) has.

From this point of view, the mixing ratio of the polyester resin (1-A) and the polyester resin (1-B) is particularly such that the polyester resin (1-B) is contained in a ratio of 20 or more, particularly 30 or more. While it is preferable to mix the polyester-based resin (1-B), the polyester-based resin (1-B) is mixed so that the polyester-based resin (1-B) is contained in a ratio of 60 or less, especially 50 or less. It is preferable.

(Other ingredients)

In order to provide hydrolysis resistance, you may mix | blend a carbodiimide compound with 1st flame-retardant resin composition. However, it does not need to mix.

Examples of the carbodiimide compound include basic structures of the following general formulas.

-(N = C = N-R-) n-

(In the above formula, n represents an integer of 1 or more. R represents another organic bonding unit. In these carbodiimide compounds, R may be any of aliphatic, alicyclic or aromatic.)

Usually, n is suitably determined between 1 and 50.

Specifically, for example, bis (dipropylphenyl) carbodiimide, poly (4,4'-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarr) Bodyimide), poly (tolylcarbodiimide), poly (diisopropylphenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide) and the like And these monomers. This carbodiimide compound is used 1 type or in combination of 2 or more types.

As a compounding quantity of a carbodiimide compound, it is preferable to mix | blend 0.1-5 mass parts with respect to 100 mass parts of 1st flame-retardant resin compositions. By mix | blending a carbodiimide compound in this range, the outstanding hydrolysis resistance can be provided without reducing heat resistance.

From such a viewpoint, it is more preferable that the compounding quantity of a carbodiimide compound is 0.5 mass% or more with respect to 100 mass parts of 1st flame-retardant resin compositions, and it is especially preferable that it is 1 mass% or more especially. Moreover, it is more preferable that it is 4 mass% or less, and it is preferable that it is 3 mass% or less especially.

Additives, such as a heat stabilizer, antioxidant, a UV absorber, a plasticizer, a nucleating agent, a light stabilizer, a pigment, and a dye, can be mix | blended with a 1st flame-retardant resin composition as needed.

Physical Properties of the First Flame Retardant Resin Composition

A 1st flame retardant resin composition can be prepared by having a flame retardance, flexibility, mechanical characteristics, and heat resistance. More specifically, regarding the flame retardancy, in the UL94 vertical combustion test defined by Underwriters Laboratories, it is possible to obtain flame retardancy satisfying the standard of VTM-0.

Regarding the mechanical properties, when the tensile strength at break is measured based on JIS C 2318, the tensile strength can be prepared at 10 MPa or more, preferably 15 MPa or more.

Regarding the flexibility, when the tensile breaking elongation is measured based on JIS C 2318, the tensile elongation can be prepared at 10% or more, preferably 20% or more.

Regarding heat resistance, when the heat of fusion of crystals ΔHm is measured based on JIS K 7121, the heat of fusion of crystals ΔHm can be prepared at 1 J / g or more, preferably 3 J / g or more.

<Use of 1st flame-retardant resin composition>

The first flame retardant resin composition can be molded into a flame retardant resin such as a film, sheet, plate, or an injection molded article. Specifically, raw materials, such as polyester resin (1-A) and melamine, and other resins and additives, such as polyester resin (1-B) as needed, are mixed directly, and it puts in an extruder or an injection molding machine, Or a method in which the raw materials are melt mixed using a twin screw extruder, extruded into strands to form pellets, and then the pellets are fed into an extruder or an injection molding machine and molded. Also in any method, it is necessary to consider the fall of the molecular weight by hydrolysis of polyester-type resin, and in order to mix uniformly, it is preferable to select the latter. So, the latter manufacturing method is demonstrated below.

Other resins and additives such as polyester-based resin (1-A) and melamine and, if necessary, polyester-based resin (1-B) are sufficiently dried to remove moisture, followed by melt mixing using a twin screw extruder, Extruded into strand shape to produce pellets.

At this time, the melting point is changed depending on the composition ratio of the polyester resin (1-A) (1-B), for example, the content ratio of terephthalic acid, the viscosity is changed depending on the blending ratio of each raw material, and the like. In consideration, it is preferable to appropriately select the melt extrusion temperature. In addition, in consideration of the sublimation temperature of melamine, it is preferable to adjust the molding temperature to a temperature range of 160 ° C or more and 220 ° C or less, particularly less than 210 ° C.

The pellet produced by the above method is sufficiently dried to remove moisture, and then a film, sheet, plate, or injection molded article can be molded by the following method.

As the forming method of the film, the sheet and the plate, in addition to the roll stretching, the tenter stretching method, the tubular method, the inflation method, a general T die cast method, a press method, or the like can be adopted as a forming method of the sheet or plate.

In addition, the molding method of an injection molded object is not specifically limited, For example, injection molding methods, such as the general injection molding method for thermoplastic resins, the gas assist molding method, and the injection compression molding method, can be employ | adopted.

In addition to the above method, 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 may be employed in accordance with the other purposes.

Moreover, one or more layers which do not contain a flame retardant can be formed in one side or both sides of the layer which consists of a 1st flame-retardant resin composition, and a laminated body can also be shape | molded.

At this time, it does not specifically limit as a layer which does not contain a flame retardant, For example, in order to provide heat resistance, a mechanical characteristic, and surface characteristics, it is preferable to form the layer which consists of said stretched polyethylene terephthalate film etc. . In addition, in the case of the purpose of improving the adhesiveness with other materials and using it for applications such as an adhesive tape, it is preferable to form an adhesive layer made of a solvent-type or emulsion-type adhesive such as rubber, acrylic, vinyl ether or the like. .

At this time, it is preferable that the thickness ratio of the layer which consists of a flame-retardant polyester-type resin composition to occupy for the whole thickness of a laminated body shall be 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 which does not impair flame retardancy and mechanical properties. From this point of view, the thickness ratio of the layer made of the flame retardant polyester resin composition to the total thickness of the laminate is particularly preferably 30% or more, particularly preferably 40% or more, particularly preferably 80% or less. Especially, it is preferable that it is 70% or less.

As a method of laminating | stacking the layer which consists of a 1st flame-retardant resin composition, and the layer which does not contain a flame retardant, it can laminate by co-extrusion, extrusion lamination, thermal lamination, dry lamination, etc.

In the case of coextrusion, the laminate is formed by joining the resins through a feed block or a multi-manifold die using a plurality of extruders. In order to provide heat resistance and mechanical strength further to a laminated body, the laminated body obtained by the said process can be extended | stretched to 1 or 2 axes using a roll method, a tenter method, a tubular method, etc.

In the case of extrusion laminate, a layer made of polyester resin (A) is extruded from a T die, an I die or the like using a single screw or twin screw extruder, and then a monolayer is formed using a roll method, a tenter method, a tubular method, or the like. Get Subsequently, a laminated body can be obtained by laminating the layer which does not contain a flame retardant on the one side or both sides of the obtained layer.

In the case of thermal lamination and dry lamination, a layer made of polyester resin (1-A) is extruded from a T die, an I die or the like using a single screw or twin screw extruder to obtain a monolayer. In addition, the same method is used to prepare a layer containing no flame retardant. Subsequently, lamination | stacking can be obtained by laminating these layers under heating or arrange | positioning an adhesive layer between layers.

Since the first flame retardant resin composition has excellent flame retardancy, mechanical properties, flexibility, and heat resistance, mobile phone parts, cable coating materials, packing materials, films and sheets for electrical insulation, materials for flat cables, and vibration damping materials It can be widely used in the field of home appliances, such as a base material for adhesive tapes, a roll, a water-order sheet, a gasket, an anti-slip material, an electrical wire covering material, and construction materials, such as an industrial use. Moreover, since it does not contain a halogen type compound or a phosphorus compound, the material excellent in safety which does not cause a problem, such as environmental pollution, can be provided.

[Second Embodiment]

The flame retardant polyester resin composition (hereinafter referred to as "second flame retardant resin composition") according to the second embodiment will be described.

By simply adding melamine to the polyester-based resin, the stress relaxation characteristics are inferior to those of the vinyl chloride-based resin. Thus, when used as a tape material or the like, for example, the melamine is easily peeled off after winding.

Therefore, in the second embodiment, the flame-retardant polyester resin composition comprising melamine as a flame retardant in a polyester resin is blended with melamine decomposed during molding so as not to cause molding defects. It is proposed a new second flame retardant resin composition having stress relaxation characteristics as described above.

That is, 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, and polyester resin (2-A) is a polyvalent car The first feature is that it contains 50 to 90 mol% of terephthalic acid as the acid component, and 70 to 100 mol% of 1,4-butanediol, ethylene glycol and diethylene glycol in total as the polyhydric alcohol component. It is a flame-retardant polyester resin composition characterized by the 2nd characteristic that the ratio of the melamine which occupies for ester resin composition is 10-60 mass%, and the ratio of phenoxy resin is 1-25 mass%.

Polyester resin containing 50-90 mol% of terephthalic acid as a polyhydric carboxylic acid component, and 70-100 mol% in total of 1, 4- butanediol, ethylene glycol, and diethylene glycol as a polyhydric alcohol component (2- Since A) has a melting point lower than that of general polyester resins such as PET and PBT, and can be molded at a temperature lower than the temperature at which melamine is decomposed, it is possible to eliminate the case where melamine is decomposed during molding to cause molding failure. Furthermore, excellent flexibility and mechanical properties can be obtained.

By blending melamine with a specific polyester resin (2-A) having such excellent flexibility and mechanical properties, it is a lower addition amount than the inorganic flame retardant which has been studied conventionally without impairing the properties originally possessed by the polyester resin, It can also impart excellent flame retardancy.

In addition, 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. Furthermore, since the phenoxy resin has a property of being easily carbonized, the carbonization promoting effect of the phenoxy resin and the combustion effect of melamine act synergistically, so that the flame retardancy can be further improved while suppressing the amount of melamine compounded. .

It will be described in detail 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))

Polyester-based resin (2-A) is a resin composition which has a polycondensation polymer of a polyhydric alcohol as a main component, and said polyester-based resin (2-A) has 50-90 mol% of terephthalic acid as a polyhydric carboxylic acid component. It is preferable that it is polyester resin which contains 70-100 mol% of 1, 4- butanediol, ethylene glycol, and diethylene glycol in total as a polyhydric alcohol component.

Since the resin composition which has polyester resin (2-A) which has such a composition as a main component has a low melting point compared with general polyester resins, such as PET and PBT, it can be shape | molded in the temperature range lower than temperature which melamine decomposes, It is possible to eliminate the case where the melamine decomposes during molding, causing molding failure. Furthermore, excellent flexibility and mechanical properties can be obtained.

From this viewpoint, it is more preferable that polyester-based resin (2-A) contains terephthalic acid 55 mol% or more, especially 60 mol% or more as polyhydric carboxylic acid component, 85 mol% or less, especially 80 mol% or less It is more preferable to contain. Moreover, as a polyhydric alcohol component, it is preferable to contain 1, 4- butanediol, ethylene glycol, and diethylene glycol in total 75 mol% or more, especially 80 mol% or more, and it is more preferable to contain 100 mol%.

However, as a polyhydric alcohol component, 1 type of 1, 4- butanediol, ethylene glycol, and diethylene glycol may be included, and 2 or more types may be contained.

The said polyester-type resin (2-A) is 1 type of polyhydric carboxylic acid besides terephthalic acid, for example, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid and other polyhydric carboxylic acids. Or it may contain 2 or more types. Furthermore, in addition to 1,4-butanediol, ethylene glycol and diethylene glycol as polyhydric alcohols, for example, propylene glycol, 1,6-hexanediol, cyclohexanediol, polyoxyene glycol, polytetramethylene ether glycol and other polyhydric compounds You may contain 1 type or 2 or more types of alcohol.

As polyester resin (2-A), you may use commercially available polyester resin. For example, Toyo Spinning Co., Ltd. "Byron" series, Nippon Synthetic Chemical Industry Co., Ltd. "Nichigo Priesuta" series, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

In addition, polyester-based resin (2-A) may be polyester-based resin which has a mixture of 2 or more types of polyester-based resin as a main component. Especially, polyester resin which contains isophthalic acid in the ratio of 5 mol% or more and less than 30 mol% in a polyhydric carboxylic acid component, and contains ethylene glycol in the ratio of 0 mol% or more and less than 50 mol% in a polyhydric alcohol component. (a-1) and isophthalic acid are contained in the polyhydric carboxylic acid component in the ratio of 30 mol% or more and 50 mol% or less, and ethylene glycol is contained in the polyhydric alcohol component in the ratio of 50 mol% or more and 100 mol% or less The mixture of polyester resin (a-2) is an especially preferable example.

By using the mixture of polyester-based resin (a-1) and (a-2) as a main component of polyester-based resin (2-A), the resin composition which has the outstanding mechanical characteristic and flexibility can be provided. In particular, by blending the polyester-based resin (a-2), the flexibility, in particular, the easiness of stretching can be enhanced.

At this time, the content ratio of isophthalic acid in the polyhydric carboxylic acid component in the polyester resin (a-1) is more preferably 7 mol% or more, particularly 10 mol% or more, and less than 25 mol%, particularly 20 It is more preferable that it is less than mol%.

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 10 mol% or more, and less than 45 mol%, particularly less than 40 mol%. More preferred.

The content ratio of isophthalic acid in the polyhydric carboxylic acid component in the polyester resin (a-2) is more preferably 33 mol% or more, particularly 35 mol% or more, and 43 mol% or less, particularly 40 mol% or less. More preferred.

Moreover, it is more preferable that the content rate of ethylene glycol in the polyhydric alcohol component in polyester-type resin (a-2) is 55 mol% or more, especially 60 mol% or more, 90 mol% or less, especially 80 mol% or less More preferred.

It is preferable that the mass mean molecular weight (the average in the case of two types) of polyester-type resin (2-A) is 10,000-300,000. If the mass average molecular weight of the polyester-based resin (2-A) is within this range, flexibility can be obtained, and furthermore, since the melt viscosity is appropriate, there is a low possibility of problems in molding processing.

From this point of view, the mass average molecular weight of the polyester resin (2-A) is particularly preferably 20,000 or more, particularly 30,000 or more, and particularly preferably 200,000 or less, particularly 150,000 or less.

In addition, a mass average molecular weight can be measured by the following method. The same applies to other resins.

Using gel permeation chromatography, solvent chloroform, solution concentration 0.2 wt / vol%, solution injection amount 200 μl, solvent flow rate 1.0 mL / min, solvent temperature 40 ° C. were measured, and the mass average molecular weight could be calculated in polystyrene conversion. have. The mass average molecular weight of the standard polystyrene used at this time is 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, 600.

It is preferable that the glass transition temperature (Tg) of polyester-type resin (2-A) is -100 degreeC-40 degreeC. If Tg of polyester-based resin (2-A) is such a temperature range, a flame-retardant polyester-based resin composition excellent in mechanical characteristics, 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 -80 ° C or higher, and particularly preferably 35 ° C or lower, particularly 30 ° C or lower.

It is preferable that the crystal melting temperature (Tm) of polyester-type resin (2-A) is 100 degreeC-190 degreeC. If Tm of polyester-based resin (2-A) is such a temperature range, a flame-retardant polyester-based resin composition excellent in mechanical characteristics, such as flexibility and tensile strength, can be prepared. In view of this, the Tm of the polyester resin (2-A) is particularly preferably 105 ° C. or higher, particularly 110 ° C. or higher, and preferably 185 ° C. or lower, particularly 180 ° C. or lower.

It is preferable that the crystal melting heat amount ((DELTA) Hm) of polyester-type resin (2-A) is 1 J / g-30 J / g. If ΔHm of the polyester-based resin (2-A) is such a temperature range, a flame-retardant polyester-based resin composition excellent in mechanical properties such as flexibility and tensile strength can be prepared. From this point of view, the ΔHm of the polyester resin (2-A) is particularly preferably 5 J / g or more, particularly 10 J / g or more, particularly 28 J / g or less, especially 25 J / g. It is preferable that it is the following.

(Melamine)

Melamine is the same as melamine used for a 1st flame-retardant resin composition, and can acquire the same effect | action. In the same manner as in the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination within the range of not impairing the effects of the present invention.

(Phenoxy resin)

Phenoxy resin is resin obtained by reaction of aromatic dihydric phenol type compounds, 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), and as a result, excellent stress relaxation Characteristics can be obtained. Furthermore, since phenoxy resin has the property of being easy to carbonize, it acts synergistically with the combustion effect of melamine, and can further improve the flame retardance of a 2nd flame-retardant resin composition, suppressing the compounding quantity of melamine.

Examples of the phenoxy resin to be used include aromatics such as hydroquinone, resorcin, 4,4'-bisphenol, 4,4'-dihydroxydiphenyl ether, bisphenol A, bisphenol F and 2,6-dihydroxynaphthalene. Dihydroxy compound, ethylene glycol diglycidyl ether propylene glycol diglycidyl ether, neopentyl glycol, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. The polyhydroxy polyether etc. which are obtained by condensing 1 type, or 2 or more types of compound chosen from an aliphatic dihydroxy compound, and epichlorohydrin are mentioned.

Typical examples of commercially available phenoxy resins include Epicoat (registered trademark) E1256, E4250, E4275 manufactured by Japan Epoxy Resin Co., Ltd., PKHH, PKHC, PKHJ, PKHB, and PKFE manufactured by InChem. Among these, epicoat (trademark) E4275 by Japan Epoxy Resin Co., Ltd. which has a bisphenol F as a main component from a viewpoint of flame retardance provision is especially preferable.

(Mixing ratio)

It is preferable that the compounding ratio of melamine in a 2nd flame-retardant resin composition is 10-60 mass%. Sufficient flame retardance can be obtained when the blending ratio of melamine in the second flame retardant resin composition is 10% by mass or more, while mechanical properties are not impaired when the blending ratio of melamine is 60% by mass or less. 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 particularly preferably 30% by mass or more. Moreover, it is especially preferable that it is 50 mass% or less, and especially it is more preferable that it is 40 mass% or less.

It is preferable that the compounding ratio of the phenoxy resin in a 2nd flame-retardant resin composition is 1-25 mass%. If the blending ratio of the phenoxy resin is within this range, the stress relaxation characteristics and the flame retardancy can be improved. From this viewpoint, it is preferable that the ratio of the phenoxy resin in a 2nd flame-retardant resin composition is 2 mass% or more, and it is still more preferable that it is 5 mass% or more especially. 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.

When manufacturing a tape from a 2nd flame-retardant resin composition especially, it is preferable to adjust the glass transition temperature (Tg) of polyester-type resin (2-A) to 40-50 degreeC by mix | blending a phenoxy resin.

(Other ingredients)

In order to provide hydrolysis resistance, you may mix | blend a carbodiimide compound with a 2nd flame-retardant resin composition. However, it does not need to mix.

The kind and compounding quantity of the carbodiimide compound mix | blended are the same as the carbodiimide compound mix | blended demonstrated in the 1st flame-retardant resin composition.

Additives, such as a heat stabilizer, antioxidant, a UV absorber, a plasticizer, a nucleating agent, a light stabilizer, a pigment, and a dye, can be mix | blended with a 2nd flame-retardant resin composition as needed.

Physical Properties of Second Flame Retardant Resin Composition

The second flame retardant resin composition can be provided with flame retardancy, flexibility, mechanical characteristics, and stress relaxation characteristics, and can be prepared by having heat resistance.

More specifically, regarding the flame retardancy, in the UL94 vertical combustion test defined by Underwriters Laboratories, it is possible to obtain flame retardancy satisfying the standard of VTM-0.

Regarding the mechanical properties, when the tensile strength at break is measured based on JIS C 2318, the tensile strength can be prepared at 10 MPa or more, preferably 15 MPa or more.

Regarding the flexibility, when the tensile breaking elongation is measured based on JIS C 2318, the tensile elongation can be prepared at 10% or more, preferably 20% or more.

Regarding the stress relaxation characteristics, when the stress relaxation ratio is measured based on JIS C 2318, the stress relaxation ratio can be prepared at 50% or more, preferably 55% or more.

Regarding heat resistance, when the heat of fusion of crystals ΔHm is measured based on JIS K 7121, the heat of fusion of crystals ΔHm can be prepared at 1 J / g or more, preferably 5 J / g or more.

<Use of 2nd flame retardant resin composition>

The second flame retardant resin composition can be molded into a flame retardant resin body such as a film, a sheet, a plate, or an injection molded article. The specific shaping | molding method in that case is the same as that of a 1st flame-retardant resin composition.

Since the second flame retardant resin composition has excellent flame retardancy, mechanical properties, and also flexibility, home appliances such as mobile phone parts, cable coating materials, packings, films and sheets for electrical insulation, flat cable materials, vibration damping materials, It can be widely used in the field of construction materials, industrial uses, such as an adhesive tape base material, a roll, an order sheet, a gasket, an anti-slip material, and an electric wire coating material. Moreover, since it does not contain a halogen type compound or a phosphorus compound, the material excellent in safety which does not cause a problem, such as environmental pollution, can be provided.

Especially, since the 2nd flame-retardant resin composition is equipped with the outstanding stress relaxation characteristic, it is especially excellent as a substitute material of what is called a vinyl tape, especially a flame-retardant vinyl tape.

[Third embodiment]

Next, the flame retardant laminate according to the third embodiment (called "third flame retardant laminate") will be described.

The third flame-retardant laminate has at least one of an A layer containing, as a main component, a mixture of polyester-based resin (3-A) and melamine having a glass transition temperature of 30 ° C. or lower and a crystal melting amount (ΔHm) of 40 J / g or lower. It is a laminated body which has B layer on the surface, and the content rate of melamine in the total mass of A layer is 10-80 mass%, It is a flame-retardant laminated body characterized by the above-mentioned.

Here, "on one surface" means forming a B layer directly on the A layer surface and forming another layer, which is a single layer or a multilayer, on the A layer surface, and forming a B layer on the other layer. It is.

According to the 3rd flame-retardant laminated body, since specific polyester resin is used and A layer has the outstanding flame retardance, even when the B layer which does not contain a flame retardant is laminated on one side or both sides, it is excellent as a whole laminated body. It can express flame retardancy.

Moreover, according to this invention, since it does not contain a halogen type compound and a phosphorus compound, the material excellent in safety which does not cause a problem, such as environmental pollution, can be provided.

<A layer>

The layer A of the third flame retardant laminate is a layer mainly composed of 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 heat of fusion of crystals (ΔHm) of 40 J / g or lower. By satisfy | filling this condition, the laminated body which is favorable in adhesiveness with polyester-type resin (3-B) and does not produce peeling between layers at the time of secondary processing and use can be provided. In addition, single resin may be sufficient as polyester-type resin (3-A) in a 3rd flame-retardant laminated body, and the mixture of two or more types of resin may be sufficient as it. As a specific example of polyester-type resin (3-A), aliphatic polyester, such as aromatic polyester lactic acid-type resin obtained by superposing | polymerizing a polyhydric carboxylic acid and a polyhydric alcohol, is mentioned.

The glass transition temperature of polyester-based resin (3-A) used for a 3rd flame-retardant laminated body is 30 degrees C or less, Preferably it is 20 degrees C or less, More preferably, it is 10 degrees C or less. Further, the heat of fusion of crystals (ΔHm) of the polyester resin (3-A) used in the third flame retardant laminate is 40 J / g or less, preferably 25 J / g or less, more preferably 20 J / g It is as follows. When the glass transition temperature of the polyester-based resin (3-A) is 30 ° C. or less and the amount of heat of fusion (ΔHm) is 40 J / g or less, the polyester-based resin (3 -B) There is no problem of peeling with.

The lower limit of the glass transition temperature of the polyester-based resin (3-A) used for the third flame retardant laminate and the lower limit of the amount of crystal melting heat (ΔHm) are not particularly limited, but the glass transition temperature is -100 ° C or higher. When the amount of heat of fusion (ΔHm) is 0 J / g or more, excellent adhesive strength with the polyester resin (3-B) is obtained in all practical temperature ranges.

As said polyester-type resin (3-A), aliphatic polyester, aromatic aliphatic polyester, polyester-type hot-melt adhesive, etc. whose glass transition temperature is 30 degrees C or less and crystal melting amount ((DELTA) Hm) are 40 J / g or less are used. Can be used alone or by mixing.

As a polyhydric carboxylic acid component used for the aliphatic and aromatic polyester obtained by superposing | polymerizing the said polyhydric carboxylic acid and a polyhydric alcohol, For example, terephthalic acid, isophthalic acid, 2-chloro terephthalic acid, 2, 5- dichloro terephthalic acid, 2-methyl Terephthalic acid, 4,4-stilbendicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, Bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid, ethylene- Aromatic dicarboxylic acids such as bis-p-benzoic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicar Aliphatic dicarboxylic acid components, such as an acid, are mentioned. These polyhydric carboxylic acid components can be used individually by 1 type or in mixture of 2 or more types.

As the polyhydric alcohol component, for example, 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, neopentylglycol, 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-hydr Oxyethyl ether). These polyhydric alcohol components can be used individually by 1 type or in mixture of 2 or more types.

As an aliphatic polyester used for a 3rd flame-retardant laminated body, the polybutylene succinate adipate copolymer obtained by superposing | polymerizing succinic acid, 1, 4- butanediol, and adipic acid ("GSPla (registered trademark) by Mitsubishi Chemical Corporation") AD series, Showa Polymer Co., Ltd. "Bionore (registered trademark) # 3000 series), etc. are mentioned.

As an aromatic aliphatic polyester used for a 3rd flame-retardant laminated body, the polybutylene adipate terephthalate copolymer obtained by superposing | polymerizing adipic acid, 1, 4- butanediol, and terephthalic acid (Ecofurex (BASF Corporation make) is registered. Trademark) "and" Eastar Bio (registered trademark) "series manufactured by Eastman Chemicals.

The weight average molecular weight of the said aliphatic polyester and aromatic aliphatic polyester is 50,000 or more normally, Preferably it is 80,000 or more, More preferably, it is 100,000 or more, The weight average molecular weight of an aromatic aliphatic polyester is 400,000 or less normally, Preferably 300,000 or less, more preferably 250,000 or less. When the weight average molecular weight of an aromatic aliphatic polyester is 50,000 or more, the fall of mechanical properties, etc. at the time of use does not occur, and when the weight average molecular weight of an aromatic aliphatic polyester is 400,000 or less, the viscosity at the time of processing is optimal. This does not cause a problem of poor thickness of the laminate or poor dispersion of melamine.

In addition, the said weight average molecular weight can be measured by the following method. That is, gel permeation chromatography was used, and chloroform was used as the solvent (solution concentration 0.2 wt / vol%, solution injection amount 200 μl, solvent flow rate 1.0 ml / min, solvent temperature 40 ° C.), and the polystyrene conversion was determined in terms of polystyrene. The weight average molecular weight of ester resin was computed. The weight average molecular weights of the used standard polystyrene are 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, and 600.

As a polyester hot melt adhesive used for a 3rd flame-retardant laminated body, the resin composition which contains polyester-based hot melt resin which is a polycondensation polymer of dibasic acid and glycol as a main component (Toron Synthetic Co., Ltd. "Aron Merto (registered trademark) PES120L) , 140H, 111E, 126E "," Byron (registered trademark) "series manufactured by Toyo Spinning Co., Ltd.) and the like. Specific examples of the dibasic acid used as the raw material monomer of the polyester-based hot melt adhesive include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid, and the like. Examples thereof 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, and the like in the molecular skeleton is preferably used.

The number average molecular weight of the polyester-based hot melt adhesive is usually 10,000 or more, preferably 12,000 or more, more preferably 15,000 or more, and the number average molecular weight is 50,000 or less, preferably 40,000 or less, and more preferably 24,000 or less. . When the mass average molecular weight of the polyester-based hot melt adhesive is in the range of 10,000 to 50,000, it has a practically sufficient mechanical property and also has a low melt viscosity.

(Melamine)

Melamine is the same as melamine used for a 1st flame-retardant resin composition, and can acquire the same effect | action. In addition, as in the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination within a range that does not impair the effect of the third flame retardant laminate.

Melamine content with respect to the total mass of the said polyester-type resin (3-A) is 20 mass% or more, Preferably it is 30 mass% or more, More preferably, it is 40 mass% or more, 80 mass% or less, Preferably It is more preferable that it is 70 mass% or less, More preferably, it is 60 mass% or less. When the content rate of melamine with respect to the total mass of polyester-type resin (3-A) is 10 mass% or more, sufficient flame retardance can be provided. On the other hand, when the content of melamine is 80% by mass or less, the mechanical properties of the layer without flame retardance do not remarkably decrease, and the mechanical properties of the laminate as a whole are not impaired.

(mixture)

The layer A of the third flame retardant laminate has a mixture of polyester-based resin (A) and melamine as a main component.

The mixture of polyester resin (A) and melamine is comprised by the above-mentioned compounding ratio, and prepares a mixture by extruding by a single screw or twin screw extruder, and forms A layer.

<B layer>

The B layer constituting the third flame retardant laminate is not particularly limited, and a material capable of constituting a known layer can be used. For example, a thermoplastic resin, a metal, etc. are mentioned.

However, it is preferable to use polyester-type resin (3-B) as long as it is a purpose to provide heat resistance, a mechanical characteristic, and surface characteristics. In addition, it is preferable to use a solvent type or emulsion type pressure-sensitive adhesive such as rubber-based, acryl-based, vinyl ether-based, etc. as long as it is intended to improve the adhesiveness with other materials and use it for the use of adhesive tape or the like.

It will be described in detail below.

Examples of the thermoplastic resin used for the B layer include low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene vinyl acetate copolymer, polyolefin resin such as polymethylpentene, polystyrene resin, polyacrylic resin, and polyvinyl chloride. And thermoplastic resins such as polyester resins, polyether resins, and polyamide resins. Especially, polyester resin is preferable in adhesiveness with A layer, and manufacture of a laminated body. Moreover, in order to improve adhesiveness with another material, you may use solvent type or emulsion type adhesives, such as rubber type, acryl type, and vinyl ether type, as B layer.

Examples of the metal used for the B layer include aluminum, nickel, gold, silver, copper, or a mixture of any one or a plurality of platinum, titanium, tantalum and tungsten.

(Polyester Resin (3-B))

As polyester-type resin (3-B) used for a 3rd flame-retardant laminated body, it is preferable that glass transition temperature is 50 degreeC or more and crystal melting amount ((DELTA) Hm) is 40 J / g or more. By satisfying this condition, a laminate having excellent heat resistance can be provided. As a specific example of polyester-type resin (3-B), aliphatic polyester, such as aromatic polyester and lactic acid-type resin obtained by superposing | polymerizing a polyhydric carboxylic acid and a polyhydric alcohol, is mentioned.

The glass transition temperature of polyester-based resin (3-B) used for a 3rd flame-retardant laminated body is 50 degreeC or more, Preferably it is 55 degreeC or more, More preferably, it is 60 degreeC or more. The amount of crystal melting heat (ΔHm) of the polyester resin (3-B) used in the third flame retardant laminate is 40 J / g or more, preferably 45 J / g or more, more preferably 50 J / g That's it. If the glass transition temperature of the polyester-based resin (3-A) is 50 ° C or higher and the crystal melting amount (ΔHm) is 40 J / g or higher, the problem of insufficient heat resistance at the time of secondary processing and use does not occur. .

The lower limit of the glass transition temperature of the polyester-based resin (3-B) used for the third flame retardant laminate and the upper limit of the amount of crystal melting heat (ΔHm) are not particularly limited, but the glass transition temperature is 100 ° C. or lower. When the amount of heat of fusion (ΔHm) is 90 J / g or less, a laminate having sufficient heat resistance is obtained.

As a polyhydric carboxylic acid component used for the aliphatic and aromatic polyester obtained by superposing | polymerizing the said polyhydric carboxylic acid and a polyhydric alcohol, For example, terephthalic acid, isophthalic acid, 2-chloro terephthalic acid, 2, 5- dichloro terephthalic acid, 2-methyl Terephthalic acid, 4,4-stilbendicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, Bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid, ethylene- Aromatic dicarboxylic acids such as bis-p-benzoic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicar Aliphatic dicarboxylic acid components, such as an acid, are mentioned. These polyhydric carboxylic acid components can be used individually by 1 type or in mixture of 2 or more types.

As the polyhydric alcohol component, for example, 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, neopentylglycol, 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-hydr Oxyethyl ether). These polyhydric alcohol components can be used individually by 1 type or in mixture of 2 or more types.

As a specific example of the polyester-type resin comprised by the said polyhydric carboxylic acid component and a polyhydric alcohol component, For example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, Polybutylene naphthalate, polyethylene terephthalate, isophthalate, etc. are mentioned. Among them, it is particularly preferable to use polyethylene terephthalate and polybutylene terephthalate in terms of heat resistance.

The weight average molecular weight of the polyester-based resin (3-B) obtained by polymerizing the polyhydric carboxylic acid and the polyhydric alcohol is usually 30,000 or more, preferably 35,000 or more, more preferably 40,000 or more, and usually 80,000 or less, preferably Is 75,000 or less, more preferably 70,000 or less. If the weight average molecular weight is 30,000 or more, an appropriate resin cohesion force can be obtained, and it can suppress that the elongation of the laminate is insufficient or brittle. On the other hand, when a weight average molecular weight is 80,000 or less, melt viscosity can be reduced and it is preferable from a viewpoint of manufacture and productivity improvement.

Examples of the lactic acid resin used in the third flame retardant laminate include poly (L-lactic acid) in which the structural unit is L lactic acid, poly (D-lactic acid) in which the structural unit is D lactic acid, polylactic acid in which the structural unit is L lactic acid and D lactic acid. (DL-lactic acid) or a mixture thereof, and may also be a copolymer of 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 it is more preferable that it is 0.5% or more and less than 2.0%. When it is less than this range, productivity is bad, and when it exceeds this range, the heat resistance of an injection molded object is hard to be obtained, and a use may be restrict | limited. Representative examples of lactic acid resins include Mitsui Chemicals, Inc. "Lasia" series, Nature Works, Inc. "Nature Works" series, and the like.

As a polymerization method of lactic acid-type resin, all well-known methods, such as a condensation polymerization method and a ring-opening polymerization method, can be employ | adopted. For example, in the polycondensation method, L-lactic acid or D-lactic acid or a mixture thereof can be directly dehydrated and condensed to obtain a lactic acid resin having an arbitrary composition.

In addition, in the ring-opening polymerization method, a polylactic acid polymer can be obtained using a catalyst selected from lactide, which is a cyclic dimer of lactic acid, if necessary using a polymerization regulator or the like. Lactides include L-lactide, a dimer of L-lactic acid, D-lactide, a dimer of D-lactic acid, and DL-lactide, which consists of L-lactic acid and D-lactic acid. By superposing | polymerizing, lactic acid-type resin which has arbitrary composition and crystallinity can be obtained.

In addition, in the range which does not impair the essential property of lactic acid-type resin, ie, the range containing 90 mass% or more of lactic acid-type resin component as needed, such as a heat resistance improvement, a non-aliphatic dicar like a terephthalic acid as a small copolymerization component. Non-aliphatic diols such as ethylene oxide adducts of acids and / or bisphenol A may be used. In addition, a small amount of chain extender such as a diisocyanate compound, an epoxy compound, an acid anhydride, or the like can be used for the purpose of increasing the molecular weight.

Examples of the other hydroxycarboxylic acid units copolymerized with lactic acid resins include optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycolic acid, 3-hydroxybutyric acid, Bifunctional aliphatic compounds such as 4-hydroxybutyric acid, 2-hydroxy n-butyric acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid Lactone, such as hydroxy carboxylic acid, caprolactone, butyrolactone, and valerolactone, is mentioned.

Ethylene glycol, 1, 4- butanediol, 1, 4- cyclohexane dimethanol, etc. are mentioned as said aliphatic diol copolymerized with lactic acid-type resin. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, suberic acid, sebacic acid, dodecane diacid, and the like.

As a preferable range of the weight average molecular weight of lactic acid-type resin, it is 50,000-400,000, Preferably it is 100,000-250,000, When it is less than this range, practical property hardly expresses, and when it exceeds, melt viscosity is too high and it is molding processability. This is inferior.

The layer thickness ratio of the A layer to the total layer thickness of the third flame retardant laminate is usually 20% or more, preferably 25% or more, more preferably 30% or more, usually 95% or less, preferably 85% Hereinafter, More preferably, it is 70% or less. Sufficient flame retardance can be provided to a flame-retardant laminated body by making layer thickness ratio of A layer into 20% or more. On the other hand, sufficient mechanical characteristics can be provided to a flame-retardant laminated body by making the layer thickness ratio of A-layer into 70% or less.

(Carbodiimide Compound)

In order to provide hydrolysis resistance to a 3rd flame-retardant laminated body, a carbodiimide compound can be mix | blended. However, it does not need to mix.

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

As a compounding quantity of the said carbodiimide compound, it is preferable to mix | blend 0.5-10 mass parts with respect to 100 mass parts of polyester-based resin (3-A) or / and polyester-based resin (3-B), and 1-5 It is more preferable to mix | blend a mass part. When it is less than such a range, the effect of providing durability is low, and when it exceeds this range, soft nitriding of a resin composition may arise, and heat resistance may be impaired.

Moreover, various additives, a resin composition, a crosslinking agent, etc. may contain in the range in which the effect of a 3rd flame-retardant laminated body is not impaired. For example, antioxidants, heat stabilizers, ultraviolet absorbers, organic particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, flame retardants, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyd resins, epoxies Resins, urea resins, phenol resins, silicone resins, rubber resins, wax compositions, melamine compounds, oxazoline crosslinkers, methylolated or alkylolated urea crosslinkers, acrylamides, polyamide resins, epoxy resins, isocyanate compounds, aziri Dean compounds, various silane coupling agents, various titanate coupling agents and the like can be used.

Among these, when inorganic particles such as silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, fine metal powder, etc. are added, It is preferable because it improves scratch resistance, scratch resistance and the like. As for the average particle diameter of an inorganic particle, 0.005-5 micrometers is preferable, More preferably, it is about 0.05-1 micrometer. Moreover, as for the addition amount, 0.05-20 weight% is preferable with respect to each of a polyester film, a resin layer, and a primer layer, More preferably, it is 0.1-10 weight%. When there is too much addition amount, moldability may fall.

Physical Properties of Third Flame Retardant Laminate

The peeling strength between A-layer and B-layer of a 3rd flame-retardant laminated body is 3 N / cm or more normally at 23 degreeC, Preferably it is 4 N / cm or more, More preferably, it is 5 N / cm or more. If A-layer and B-layer are 3 N / cm or more, it can be used for various uses as a laminated body integrally.

The tensile strength of the third flame retardant laminate is usually 80 MPa or more, preferably 100 MPa or more, and more preferably 120 MPa or more. If the tensile strength of a flame-retardant laminated body is 80 Mpa or more, the fall of workability at the time of secondary processing, breakage of the laminated body at the time of use, etc. will not arise.

Tensile elongation of a 3rd flame-retardant laminated body is 80% or more normally, Preferably it is 100% or more, More preferably, it is 120% or more. If the tensile elongation of a flame-retardant laminated body is 80% or more, breakage of a laminated body at the time of use, etc. will not occur.

<The manufacturing method of the third flame-retardant laminated body>

Next, the manufacturing method of a 3rd flame-retardant laminated body is demonstrated.

Here, although the manufacturing method of the 3rd flame-retardant laminated body of a film or sheet form is demonstrated, it is not limited to the example demonstrated next.

As a lamination | stacking method of A-layer and B-layer in a 3rd flame-retardant laminated body, it can laminate | stack by co-extrusion, extrusion lamination, thermal lamination, dry lamination, etc.

In the case of coextrusion, the raw material constituting the A layer is mixed and kneaded to prepare a resin composition, and the resin composition (a) is extruded by a single screw or twin screw extruder, while using a different extruder, the B layer The raw materials constituting the present invention are mixed and kneaded to prepare a resin composition, the resin composition (b) is extruded by a single screw or twin screw extruder, and the resins are joined through a feed block or a multi-manifold die to form a third flame retardant laminate. Can be molded. Moreover, in order to provide heat resistance and mechanical strength, you may extend | stretch the laminated | multilayer film obtained by the said process to 1 axis | shaft or 2 axis | shaft using a roll method, a tenter method, a tubular method, etc.

In the case of extrusion laminate, the raw material constituting the B layer is mixed and kneaded to prepare a resin composition (b), and extruded from a T die, an I die or the like using a single screw or twin screw extruder, and then a roll method, a tenter method, a tube The film used as a B layer is obtained using a blur method. Next, the raw material which comprises A layer is mixed and kneaded, the resin composition (a) is prepared, the resin composition (a) is extruded with a single screw or twin screw extruder, and the said B is simultaneously cast with the film used as A layer. By laminating the film used as a layer, a 3rd flame-retardant laminated body can be shape | molded. 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 a resin composition (a), and the resin composition (a) is extruded from a T die, an I die or the like by a single screw or twin screw extruder. While obtaining the film used as A layer, the raw material which comprises B layer is mixed and kneaded, the resin composition (b) is prepared, and a resin composition (b) is made from a T die, an I die, etc. by a single screw or a twin screw extruder. It extrudes and the film used as B layer is obtained.

Subsequently, the third flame-retardant laminate can be formed by heating the film to be the A layer and the film to be the B layer, or disposing the adhesive layer between the layers, and laminating both. The stretching of the third flame retardant laminate is the same as in the case of coextrusion.

Moreover, in order to further improve the adhesiveness between A-layer and B-layer, corona discharge treatment may be given to the A-layer side surface of B-layer, and an anchor coat layer may be formed on B-layer.

As an adhesive agent for anchor coats used for an anchor coat layer, adhesive agents, such as polyester type, a polyurethane type, an acryl type, PVC-vinyl acetate copolymerization system, are mentioned. In addition, the roll coat method, the gravure coat method, etc. can be used for application | coating of the adhesive agent for anchor coats. In addition, although the thickness of an anchor coat layer can be adjusted suitably, it is preferable to set it as the range of 0.1 micrometer-5 micrometers from a flame retardance and adhesiveness.

In addition, when extending | stretching a 3rd flame-retardant laminated body, in order to suppress thermal contraction of a laminated body in any case, it is preferable to perform a heat set in the state which grasped the sheet | seat after extending | stretching. Usually, in a roll method, after extending | stretching, a heat set is performed by making it contact with a heating roll, and in a tenter method, a heat set is performed in the state which grasped the sheet | seat with a clip. Although a heat set temperature changes with kinds of resin to be used, it is preferable to perform a heat set at the temperature about 10-100 degreeC lower than melting | fusing point of resin to be used. Moreover, in order to further improve the ink adhesiveness of the polyester resin layer used as both outer layers, surface treatment, such as a discharge treatment, such as a corona treatment, and a flame treatment, can be performed.

<Use of the third flame retardant laminate>

Since the third flame retardant laminate has excellent flame retardancy, mechanical properties, and surface properties, the third flame retardant laminate can be used for applications such as electrical insulation materials, membrane switch circuit printing substrates, copier inner members, planar heating element substrates, and FPC reinforcing plates.

[Fourth flame retardant laminate]

Next, the flame retardant laminate according to the fourth embodiment (hereinafter referred to as "fourth flame retardant laminate") will be described.

In the prior art, in order to obtain a high flame retardancy that passes VTM-0 in the UL94 vertical combustion test, it is necessary to blend a large amount of flame retardant in the adhesive layer, and the adhesiveness between the adhesive layer and the metal is lowered. There was a problem such as becoming. Moreover, in order 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 the problems of the prior art, the present invention is intended to provide a new flame retardant resin laminate for metal bonding, which does not contain a halogen compound and a phosphorus compound, and has both metal adhesion and flame retardancy.

That is, this invention is the 4th flame-retardant laminated body which is a flame-retardant resin laminated body for metal bonding which combines metal adhesiveness and flame retardancy, The polyester resin (4-A), melamine, and phenoxy whose glass transition temperature is -80-30 degreeC It has A layer which consists of a resin composition (a) which has a mixture of shi resin as a main component, On this A layer, glass transition temperature is 50-120 degreeC, and crystal melting heat amount ((DELTA) Hm) is 40-100 J / g. It is a resin laminated body which has B layer which consists of a resin composition (b) which has polyester resin (4-B) as a main component, and the ratio of the melamine which occupies in the resin composition (a) which comprises A layer is 20-80 mass%. Moreover, the ratio of the phenoxy resin in a resin composition (a) is 1-30 mass%, It proposes the flame-retardant resin laminated body for metal bondings characterized by the above-mentioned.

According to the fourth flame retardant laminate, flame retardancy is achieved by blending melamine mainly for improving flame retardancy and phenoxy resin mainly for improving adhesion with a metal to specific polyester resins constituting the adhesive layer (A layer). In addition, the adhesion between the adhesive layer (A layer) and the metal can be significantly increased. Moreover, since it does not contain a halogen type compound and a phosphorus compound, the material excellent in safety which does not cause a problem, such as environmental pollution, can be provided.

Since the phenoxy resin is hydrogen-bonded with moisture present on the metal surface, it is not only excellent in adhesiveness with the metal but also compatible with the polyester-based resin, and therefore, it is used in the polyester-based resin (4-A). By mix | blending, adhesiveness with a metal can be improved without reducing flame retardance.

In addition, since melamine generates a non-combustible gas at the time of combustion, not only can the flame-retardant adhesive layer be flame-retarded, but also the outer layer (B layer) which does not contain a flame retardant can be flame-retarded, so that the flame retardancy of the whole laminate is exceptional. It can increase.

Furthermore, by combining phenoxy resin and melamine in combination with the polyester resin (4-A), a synergistic effect can be obtained without canceling each other's characteristics.

On the other hand, a 4th flame-retardant laminated body is polyester-based resin (4-B) on the A layer which consists of a resin composition (a) which has a mixture of polyester-based resin (4-A), melamine, and phenoxy resin as a main component. It is a laminated body provided with the B layer which consists of resin composition (b) which has) as a main component.

Here, "on A layer" means the case including laminating the B layer via another layer on the A layer, in addition to laminating the B layer directly on the A layer.

<A layer>

In the fourth flame retardant laminate, the layer A has a role of an adhesive layer, and the layer A is a resin composition containing a mixture of polyester resin (4-A), melamine and phenoxy resin as a main component (a ) Layer.

(Polyester-Based Resin (4-A))

It is important that polyester-type resin (4-A) is resin whose glass transition temperature is -80 degreeC-30 degreeC. When the glass transition temperature of polyester-type resin (4-A) is -80 degreeC-30 degreeC, it can be set as the laminated body which has the outstanding mechanical characteristic in the wide range from low temperature to normal use temperature.

From such a viewpoint, it is especially preferable that the glass transition temperature of polyester-type resin (4-A) is -70 degreeC or more, and it is more preferable especially -60 degreeC or more. Moreover, it is especially preferable that it is 20 degrees C or less, and especially it is more preferable that it is 10 degrees C or less.

It is preferable that polyester-based resin (4-A) is resin whose crystal melting heat amount ((DELTA) Hm) is 5-30 J / g. When the heat of fusion of crystals (ΔHm) of the polyester-based resin (4-A) is 5 to 30 J / g, it may be a laminate having sufficient adhesiveness and heat resistance at the time of molding, secondary processing and use.

From this point of view, the heat of fusion of crystals (ΔHm) of the polyester resin (4-A) is particularly preferably 8 J / g or more, and more preferably 10 J / g or more. Moreover, it is especially preferable that it is 25 J / g or less, and especially it is more preferable that it is 20 J / g or less.

As polyester resin (4-A), 1 type, or 2 or more types of mixed resin can be used among aliphatic polyester, aromatic aliphatic polyester, and polyester type hot melt adhesive. That is, a polyester resin (4-A) may be a single resin, or a mixture of two or more kinds of resins may be used.

Examples of the aliphatic polyester used as the polyester resin (4-A) include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid, and 1,4. 1 or 2 or more aliphatic dicarboxylic acids in 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, neopentylglycol, 1,5-pentanediol , 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A and tetra The copolymer polyester which consists of 1 type, or 2 or more types of polyhydric alcohols in bromobisphenol A-bis (2-hydroxyethyl ether) is mentioned.

More specifically, a copolymer of succinic acid and 1,4-butanediol ("GSPla" AZ series by Mitsubishi Chemical Corporation, "Bionore" # 1000 series by Showa Polymer Corporation), succinic acid, 1,4-butanediol and adipic And aliphatic polyesters such as polybutylene succinate adipate copolymers ("GSPla" AD series manufactured by Mitsubishi Chemical Corporation, "Bionore" # 3000 series manufactured by Showa Polymer Corporation), which are copolymers of acids.

As an aromatic aliphatic polyester used as polyester-type resin (4-A), terephthalic acid, isophthalic acid, 2-chloro terephthalic acid, 2,5- dichloro terephthalic acid, 2-methyl terephthalic acid, 4,4-stilbendicarboxylic acid Acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthraceneca One or two of leric acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid and ethylene-bis-p-benzoic acid More aromatic dicarboxylic acids,

One or two or more aliphatic dicarboxylic acids among succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Mountain Range,

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, neopentylglycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A and tetrabromobisphenol A-bis (2-hydroxyethyl ether) The copolyester which consists of the above polyhydric alcohol is mentioned.

More specifically, the polybutylene adipate-terephthalate copolymer obtained by superposing | polymerizing adipic acid, 1, 4- butanediol, and terephthalic acid (the "Ecofurex" series by BASF Corporation, "Eastar Bio" by Eastman Chemicals Corporation) Aromatic aliphatic polyesters, such as the series), are mentioned.

Among the above, at least one polyhydric carboxylic acid component selected from succinic acid, adipic acid, terephthalic acid and isophthalic acid, and 1,4-butanediol, 1,6-hexanediol, ethylene glycol and polytetramethylene ether glycol Co-polyester containing at least 1 type of polyhydric-alcohol component becomes preferable as polyester-type resin (4-A).

It is preferable that the mass mean molecular weights of these aliphatic polyester and aromatic aliphatic polyester are 50,000-400,000. If the mass average molecular weight of these polyesters is 50,000 or more, the problem that a laminated body will be damaged by lack of flame retardance or a lack of mechanical strength does not arise. Moreover, if the mass mean molecular weight is 400,000 or less, the problem of molding failure due to too high a viscosity of the resin does not occur.

From this point of view, the mass average molecular weight of the aliphatic polyester and the aromatic aliphatic polyester is particularly preferably 80,000 or more, and particularly preferably 100,000 or more. Moreover, it is especially preferable that it is 300,000 or less, and especially it is more preferable that it is 250,000 or less.

In addition, a mass average molecular weight can be measured by the following method. The same applies to other resins.

Using gel permeation chromatography, solvent chloroform, solution concentration 0.2 wt / vol%, solution injection amount 200 μl, solvent flow rate 1.0 mL / min, solvent temperature 40 ° C. were measured, and the mass average molecular weight could be calculated in polystyrene conversion. have. The mass average molecular weight of the standard polystyrene used at this time is 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, 600.

As a polyester type hot melt resin used as polyester resin (4-A), the resin composition etc. which contain polyester type hot melt resin which is a polycondensation polymer of dibasic acid and glycol as a main component are mentioned.

Specific examples of the dibasic acid used as the raw material monomer of the polyester-based hot melt adhesive include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid, and the like. Examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol.

Among the above-mentioned, the hot-melt resin which consists of polyester resin which contains adipic acid, 1, 4- butanediol, etc. in a molecular skeleton is used preferably.

As a commercially available polyester-type hot melt resin, the Nippon Synthetic Chemical Industry Co., Ltd. "Nichigo Piesta" series and Toyo Spinning Co., Ltd. "Byron" series are mentioned, for example.

It is preferable that the mass mean molecular weights of a polyester type hot melt adhesive agent are 20,000-120,000. If it is this range, since it has practically sufficient mechanical characteristics, and since melt viscosity is suitable, it is unlikely that a problem arises in a shaping | molding process.

From such a 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. Moreover, it is especially preferable that it is 110,000 or less, and especially it is more preferable that it is 100,000 or less.

(Melamine)

Melamine is the same as the melamine used for a 1st flame-retardant resin composition, and the same effect can be acquired. In addition, similar to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination within a range that does not impair the effect of the fourth flame retardant laminate.

Since melamine generates incombustible gas at the time of combustion, not only can it not only flame-retardant A layer but also flame-retardant B layer, the flame retardance of the whole 4th flame-retardant laminated body can be improved significantly.

(Phenoxy resin)

The phenoxy resin is the same as the phenoxy resin used for the second flame retardant resin composition, and the same effect can be obtained.

(Mixing ratio)

It is important that the compounding ratio of melamine which occupies in the resin composition (a) which comprises A layer is 20-80 mass%. Sufficient flame retardance can be obtained as the compounding ratio of melamine which occupies in the resin composition (a) which comprises A layer is 20 mass% or more. 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 are not impaired.

From such a viewpoint, it is preferable that the mixture ratio of the melamine which occupies in the resin composition (a) which comprises A layer is 30 mass% or more, and it is still more preferable that it is 40 mass% or more especially. Moreover, it is preferable that it is 70 mass% or less, and especially it is more preferable that it is 60 mass% or less.

About the compounding quantity of phenoxy resin, it is important that the ratio of the phenoxy resin in the resin composition (a) which comprises A layer is 1-30 mass%. When it is less than this range, the effect of improving adhesiveness with a metal is hardly obtained, and when it exceeds this range, mechanical properties, especially impact resistance may fall.

From such a viewpoint, it is preferable that the ratio of the phenoxy resin in the resin composition (a) which comprises A layer is 5 mass% or more, and it is preferable that it is 20 mass% or less.

<B layer>

B layer is a layer which consists of resin composition (b) which has polyester-based resin (4-B) as a main component.

(Polyester Resin (4-B))

As polyester-based resin (4-B), it is important to use polyester-based resin whose glass transition temperature is 50-120 degreeC, and whose crystal melting heat amount ((DELTA) Hm) is 40-100 J / g. By satisfying this condition, a laminate having excellent heat resistance can be provided.

It is important that the glass transition temperature of polyester-type resin (4-B) is 50-120 degreeC as mentioned above. If the glass transition temperature of polyester-type resin (4-B) is 50-120 degreeC, it can be set as the laminated body which has the outstanding moldability and the outstanding heat resistance at the time of use.

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 especially it is more preferable that it is 100 degrees C or less.

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

From this viewpoint, it is preferable that the amount of crystal melting heat (ΔHm) of the polyester resin (4-B) is 45 J / g or more, and more preferably 50 J / g or more. Moreover, it is preferable that it is 90 J / g or less, and especially it is more preferable that it is 80 J / g or less.

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

At this time, as a polyhydric carboxylic acid component used for an aliphatic polyester or an aromatic polyester, for example, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4- Stilbendicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl Methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid, ethylene-bis-p-benzoic acid, etc. Aliphatic dicarboxylic acids such as aromatic dicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid A carboxylic acid component can be mentioned. These polyhydric carboxylic acid components can be used individually by 1 type or in mixture of 2 or more types.

As the polyhydric alcohol component, for example, 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, neopentylglycol, 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-hydr Oxyethyl ether). These polyhydric alcohol components can be used individually by 1 type or in mixture of 2 or more types.

As a specific example of the polyester-type resin comprised by the said polyhydric carboxylic acid component and a polyhydric alcohol component, For example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, Polybutylene naphthalate, polyethylene terephthalate, isophthalate, etc. are mentioned. Among them, it is particularly preferable to use polyethylene terephthalate and polybutylene terephthalate in terms of heat resistance.

It is preferable that the mass mean molecular weights of polyester-type resin (4-B) are 30,000-80,000. If the mass average molecular weight of polyester-type resin (4-B) is 30,000 or more, appropriate resin cohesion force will be obtained and it can suppress that the elongation of a laminated body is insufficient or embrittled. On the other hand, if it is 80,000 or less, melt viscosity can be reduced and it is preferable from a viewpoint of manufacture and productivity improvement.

From such a viewpoint, the mass average molecular weight of the polyester resin (4-B) is particularly preferably 35,000 or more, more preferably 40,000 or more. Moreover, it is especially preferable that it is 75,000 or less, and especially it is more preferable that it is 70,000 or less.

B layer may be comprised by the stretched film, In that case, it is preferable that it is comprised by the biaxially stretched film.

&Lt; Other components >

In a 4th flame-retardant laminated body, you may mix | blend a carbodiimide compound with the resin composition (a) which comprises A layer, and the resin composition (b) which comprises B layer in order to provide hydrolysis resistance. However, it does not need to mix.

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

As a compounding quantity of a carbodiimide compound, it is preferable to mix | blend 0.5-10 mass parts with respect to 100 mass parts of polyester resins (4-A) or 100 mass parts of polyester resins (4-B), and 1-5 It is more preferable to mix | blend a mass part. When it is less than such a range, the effect of providing durability is low, and when it exceeds this range, soft nitriding of a resin composition may arise, and heat resistance may be impaired.

<Layer thickness>

It is preferable that the layer thickness ratio of A layer with respect to the total layer thickness of a 4th flame-retardant laminated body is 20 to 70%. Sufficient flame retardance can be provided to a 4th flame-retardant laminated body by making layer thickness ratio of A layer into 20% or more. On the other hand, sufficient mechanical characteristics can be provided to a 4th flame-retardant laminated body by making the layer thickness ratio of A layer into 70% or less.

From this point of view, the layer thickness ratio of the A layer to the total layer thickness of the fourth flame retardant laminate is particularly preferably 25% or more, more preferably 30% or more. Moreover, it is especially preferable that it is 60% or less, and it is still more preferable that it is 50% or less especially.

In addition, the 4th flame-retardant laminated body may be equipped with layers other than A layer and B layer. For example, another layer may be interposed between A-layer and B-layer, and the other layer may be provided in the outer side (opposite side to A-layer) of B-layer.

The thickness of a 4th flame-retardant laminated body is not specifically limited, It can adjust to the thickness according to each use, such as a film, a sheet, a panel.

<Peel strength>

In a 4th flame-retardant laminated body, it is preferable that peeling strength between A-layer and B-layer is 3 N / cm or more at 23 degreeC, Especially 4 N / cm or more, It is preferable that it is 5 N / cm or more especially.

In addition, in the case where the A layer of the fourth flame retardant laminate is bonded to the metal, assuming that a wiring cable is manufactured, for example, the peel strength of the A layer and the metal (especially tin-plated copper foil) is 5 N at 23 ° C. It becomes / cm or more, Especially preferably, it is 6N / cm or more, Especially preferably, it is 7N / cm or more.

Especially, if peeling strength between A-layer and B-layer is 3 N / cm or more, and peeling strength of A-layer and metal conductor (especially tin-plated copper foil) is 5 N / cm or more, it can be used for various uses as a laminated body. It is more preferable because it can.

<Manufacturing Method>

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

<Use>

The fourth flame retardant laminate can obtain not only flame retardancy, in particular flame retardancy satisfying the VTM-0 specification of the criterion of the UL94 vertical combustion test UL94VTM, but also excellent metal adhesiveness with respect to metals, especially copper. Therefore, it can use suitably as a coating resin film which coat | covers a metal conductor, for example. That is, a wiring cable can be manufactured by using two fourth flame-retardant laminates, arranging a metal conductor between these A layers, and joining two fourth flame-retardant laminates together.

Especially, since a 4th flame-retardant laminated body can obtain not only the outstanding flame retardance and metal adhesiveness as mentioned above but also the outstanding flexibility and excellent heat resistance, it is especially suitable for flat cables.

In addition, since the fourth flame retardant laminate has excellent adhesion to metals other than copper, such as silver, gold, platinum, iron, stainless steel, steel or alloys thereof, the fourth flame retardant laminate is not only used for wiring cables as described above, It can also use suitably for the other use which requires a flame retardance and metal adhesiveness. Examples include reinforcement plates and labels. A reinforcement board means the board affixed on the edge part of a wiring cable here.

[Fifth flame retardant laminate]

Next, the flame retardant laminate according to the fifth embodiment (hereinafter referred to as "the fifth flame retardant laminate") will be described.

The fifth flame retardant laminate provides a laminate which does not contain a halogen compound and a phosphorus compound, has excellent flame resistance, and also has excellent heat resistance and mechanical properties.

That is, the 5th flame-retardant laminated body is a poly which has a glass transition temperature of 60 degreeC or more on at least one side of A-layer which has a mixture of polyester resin (5-A), melamine, and a crosslinking agent whose glass transition temperature is 20 degrees C or less. A laminate having a B layer containing ester resin (5-B) as a main component, wherein the gel fraction of the laminate is 15% by mass to 55% by mass, and the proportion of melamine in the laminate is 10% by mass or more. It is 40 mass% or less, It is a heat resistant flame-retardant laminated body characterized by the above-mentioned.

(Polyester-Based Resin (5-A))

It is important that polyester-type resin (5-A) is 20 degrees C or less in glass transition temperature. By satisfy | filling this condition, adhesiveness with the B layer which consists of polyester-type resin (5-B) whose glass transition temperature is 60 degreeC or more is favorable, and it does not produce peeling between layers at the time of secondary processing and use. In addition to providing a laminate, it is possible to provide a laminate having excellent mechanical strength. In addition, single resin may be sufficient as polyester-type resin (5-A), and the mixture of two or more types of resin may be sufficient as it.

The glass transition temperature of polyester-based resin (5-A) used for a 5th flame-retardant laminated body is 20 degrees C or less, Preferably it is 10 degrees C or less, More preferably, it is 0 degrees C or less. If the glass transition temperature of the polyester-based resin (5-A) is 20 ° C. or less, there is a problem of peeling with the B layer made of the polyester-based resin (5-B) during molding, secondary processing, and use. Not only does it occur, but excellent mechanical properties (particularly tensile elongation) can be imparted to the flame retardant laminate.

In addition, the lower limit of the glass transition temperature of polyester-type resin (5-A) is not specifically limited, If it is -100 degreeC or more, as polyester-based resin (5-B) in all practical temperature ranges. Excellent adhesive strength with the formed B layer is obtained.

Further, if the amount of heat of fusion (ΔHm) of the polyester-based resin (5-A) is 40 J / g or less, preferably 35 J / g or less, more preferably 30 J / g or less, furthermore, The adhesive strength can be improved.

As said polyester-type resin (5-A), it can use by aliphatic polyester whose aromatic glass transition temperature is 20 degrees C or less, aromatic aliphatic polyester, or polyester type hot melt adhesive etc. individually or in mixture.

As said aliphatic polyester, polybutylene succinate obtained by superposing | polymerizing succinic acid and 1, 4- butanediol ("GSPla" AZ series by Mitsubishi Chemical Corporation, "Bionore" # 1000 series by Showa Polymer Corporation), etc. are mentioned. Can be.

As said aliphatic polyester, the polybutylene succinate adipate copolymer obtained by superposing | polymerizing succinic acid, 1, 4- butanediol, and adipic acid ("GSPla" AD series by Mitsubishi Chemical Corporation, "Biono" by Showa Polymer Corporation) # 3000 series), and the like.

As said aromatic aliphatic polyester, the polybutylene adipate terephthalate copolymer obtained by superposing | polymerizing adipic acid, 1, 4- butanediol, and terephthalic acid (the "Eco-Frex" series by BASF Corporation, "manufactured by Eastman Chemicals" Eastar Bio "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, and the upper limit of the weight average molecular weight of the aromatic aliphatic polyester is 400,000 or less, preferably Is 300,000 or less, more preferably 250,000 or less. When the weight average molecular weight of an aromatic aliphatic polyester is 50,000 or more, the fall of mechanical properties, etc. at the time of use does not occur, and when the weight average molecular weight of an aromatic aliphatic polyester is 400,000 or less, the viscosity at the time of processing is optimal. This does not cause a problem of poor thickness of the laminate or poor dispersion of melamine.

In addition, the said weight average molecular weight is a value measured by the following method. That is, gel permeation chromatography was used, and chloroform was used as the solvent (solution concentration 0.2 wt / vol%, solution injection amount 200 μl, solvent flow rate 1.0 ml / min, solvent temperature 40 ° C.), and the polystyrene conversion was determined in terms of polystyrene. The weight average molecular weight of ester resin can be calculated. The weight average molecular weights of the used standard polystyrene are 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, and 600.

As said polyester-type hot melt adhesive agent, the resin composition (The Toyo Spinning company "Byron" (registered trademark) series which contains polyester-based hot melt resin which is a polycondensation polymer of dibasic acid and glycol as a main component, "Nichi" Goforiesta "series), etc. are mentioned. Specific examples of the dibasic acid used as the raw material monomer of the polyester-based hot melt adhesive include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid, and the like. Examples thereof 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 and the like in the molecular skeleton is preferably used.

The lower limit of the weight average molecular weight of the polyester-based 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 weight average molecular weight is 120,000 or less, preferably 110,000 or less, more preferably 100,000. It is as follows. If it is the range of the weight average molecular weights 20,000 or more and 120,000 or less of a polyester type hot melt adhesive agent, since it has practically sufficient mechanical characteristics and moderate melt viscosity, it is unlikely that a problem arises in molding processing.

(Melamine)

Melamine is the same as the melamine used for a 1st flame-retardant resin composition, and the same effect can be acquired. In addition, similar to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination within a range that does not impair the effect of the fifth flame retardant laminate.

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, 40% by mass or less, preferably 35% by mass or less, more preferably. More preferably, it is 30 mass% or less. When the content rate of melamine in the resin composition which comprises a 5th flame-retardant laminated body is 10 mass% or more, sufficient flame retardance can be provided. On the other hand, when the content rate of melamine is 40 mass% or less, the mechanical properties of the layer without flame retardance do not remarkably decrease, and mechanical properties as a whole laminate are not impaired.

In addition, when using the surface-treated melamine, you may mix and use the surface-treated melamine and the surface-treated melamine, and may use only the surface-treated melamine. As for the content rate of the surface-treated melamine, with respect to the mass of all the melamine components of a 5th flame-retardant laminated body, a lower limit is 10 mass% or more, Preferably it is 20 mass% or more, More preferably, it is 40 mass% or more, and an upper limit is 100 It is mass% or less, Preferably it is 80 mass% or less, More preferably, it is 60 mass% or less. If it is 10 mass% or more, excellent dispersibility can be provided by surface treatment, and if it is 100 mass% or less, the problem of the fall of a mechanical property and a viscosity increase does not arise.

(Bridge)

As a crosslinking agent used for a 5th flame-retardant laminated body, the compound whose molecular weight which has two or more functional groups, such as an acryl group, a methacryl group, an allyl group, and a vinyl group, in a molecule | numerator is generally 2000 or less can be used preferably. Specifically, diallyl isocyanate, triallyl isocyanate, dimethallyl isocyanate, trimethallyl isocyanate, diallyl monoglycidyl isocyanate, 1,4-butanediol dimethacrylate, polyethylene glycol methacrylate, pentaerythritol di Methacrylate, dipentaerythritol hexaacrylate, trimethylolpropane acrylate, divinylbenzene, trivinylbenzene, hexamethylbenzene and the like.

As a compounding quantity of the said crosslinking agent, it is preferable that the ratio of the crosslinking agent which occupies for A-layer is 0.1 mass% or more and 5 mass% or less, It is more preferable that they are 0.5 mass% or more and 4 mass% or less, It is more preferable that they are 1 mass% or more and 3 mass% or less. desirable. By mix | blending a crosslinking agent in such a range, sufficient gel fraction can be obtained and it can provide the heat resistance excellent in a laminated body.

(Polyester Resin (5-B))

As polyester resin (5-B), it is important that glass transition temperature is 60 degreeC or more. By satisfying this condition, a laminate having excellent heat resistance can be provided. As a specific example of polyester-type resin (5-B), aliphatic polyester, such as aromatic polyester and lactic acid-type resin obtained by superposing | polymerizing a polyhydric carboxylic acid and a polyhydric alcohol, is mentioned.

The lower limit of the glass transition temperature of polyester resin (5-B) is 60 degreeC or more, Preferably it is 65 degreeC or more, More preferably, it is 70 degreeC or more. If the lower limit of the glass transition temperature of polyester-type resin (5-B) is 60 degreeC or more, the problem of the lack of heat resistance at the time of secondary processing and at the time of use will not arise.

In addition, the lower limit of the glass transition temperature of polyester-type resin (5-B) is not specifically limited, If the said glass transition temperature is 100 degrees C or less, the laminated body provided with sufficient flame retardance, heat resistance, and a mechanical characteristic will be obtained.

In addition, if the lower limit of the heat of fusion of crystals (5-B) of the polyester-based resin (5-B) is 45 J / g or more, preferably 50 J / g or more, and more preferably 55 J / g or more, the heat resistance An excellent laminate can be provided.

Here, as a polyhydric carboxylic acid component used for the aliphatic and aromatic polyester obtained by superposing | polymerizing the said polyhydric carboxylic acid and a polyhydric alcohol, For example, terephthalic acid, isophthalic acid, 2-chloro terephthalic acid, 2,5- dichloro terephthalic acid, 2 -Methyl terephthalic acid, 4,4-stilbendicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bis Benzoic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid, Aromatic dicarboxylic acids such as ethylene-bis-p-benzoic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane Aliphatic dicarboxylic acid components, such as dicarboxylic acid, are mentioned. These polyhydric carboxylic acid components can be used individually by 1 type or in mixture of 2 or more types.

As the polyhydric alcohol component, for example, 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, neopentylglycol, 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-hydr Oxyethyl ether). These polyhydric alcohol components can be used individually by 1 type or in mixture of 2 or more types.

As a specific example of the polyester-type resin comprised by the said polyhydric carboxylic acid component and a polyhydric alcohol component, For example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, Polybutylene naphthalate, polyethylene terephthalate isophthalate, polytrimethylene terephthalate, etc. are mentioned. Among them, it is particularly preferable to use polyethylene terephthalate and polybutylene terephthalate in terms of heat resistance.

The weight average molecular weight of the polyester-based resin (5-B) obtained by polymerizing the polyhydric carboxylic acid and the polyhydric alcohol is usually 30,000 or more, preferably 35,000 or more, more preferably 40,000 or more, and usually 80,000 or less, preferably Is 75,000 or less, more preferably 70,000 or less. If the weight average molecular weight is 30,000 or more, an appropriate resin cohesion force can be obtained, and it can suppress that the elongation of the laminate is insufficient or brittle. On the other hand, when a weight average molecular weight is 80,000 or less, melt viscosity can be reduced and it is preferable from a viewpoint of manufacture and productivity improvement.

<Layer composition>

Although the thickness ratio of the A layer with respect to the total layer thickness of a 5th flame-retardant laminated body can be adjusted suitably so that the ratio of melamine which may occupy in the resin composition which comprises a whole laminated body may be 10 mass% or more and 40 mass% or less, It is usually 20% or more, preferably 25% or more, more preferably 30% or more, 70% or less, preferably 60% or less, and more preferably 50% or less. By setting the layer thickness ratio of the layer A 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 provide hydrolysis resistance to a 5th flame-retardant laminated body, a carbodiimide compound can be mix | blended. However, it does not need to mix.

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

As a compounding quantity of the said carbodiimide compound, it mix | blends with the ratio of 0.5 mass part or more and 10 mass parts or less with respect to 100 mass parts of polyester resin (5-A) or / and polyester resin (5-B). It is preferable to mix | blend at the ratio of 1 mass part or more and 5 mass parts or less. When it is less than such a range, the effect of providing durability is low, and when it exceeds this range, soft nitriding of a resin composition may arise, and heat resistance may be impaired.

Moreover, various additives, a resin composition, a crosslinking agent, etc. may contain in the range in which the effect of a 5th flame-retardant laminated body is not impaired. For example, antioxidants, heat stabilizers, ultraviolet absorbers, organic particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, flame retardants, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyd resins, epoxies Resins, urea resins, phenol resins, silicone resins, rubber resins, wax compositions, melamine compounds, oxazoline crosslinkers, methylolated or alkylolated urea crosslinkers, acrylamides, polyamide resins, epoxy resins, isocyanate compounds, aziri Dean compounds, various silane coupling agents, various titanate coupling agents and the like can be used.

Among these, when an inorganic particle, for example, silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, fine metal powder or the like is added, It is preferable because it improves scratch resistance, scratch resistance and the like. It is preferable that it is 0.005 micrometer or more and 5 micrometers or less, and, as for the average particle diameter of an inorganic particle, it is more preferable that they are 0.05 micrometer or more and 1 micrometer or less. Moreover, it is preferable to mix | blend the addition amount in the ratio of 0.05 mass% or more and 20 weight% or less with respect to each of the resin composition which comprises A layer, B layer, or the resin composition which comprises the adhesive layer between A layer and B layer, It is more preferable to mix | blend in the ratio of 0.1 mass% or more and 10 weight% or less.

When there is too much addition amount, moldability may fall.

<Manufacturing Method>

The fifth flame retardant laminate can be produced in the same manner as the third flame retardant laminate described above.

However, a 5th flame-retardant laminated body can extend | stretch A layer and B layer, A layer, or B layer. The draw ratio of the A layer and / or the B layer is 1.5 times, preferably 3 times, more preferably 5 times in the MD (length direction), 1.5 times in the TD (horizontal direction), preferably 3 times, and more. Preferably 5 times. Moreover, although extending | stretching can be performed by MD and / or TD, it is preferable to extend | stretch to MD and TD from a viewpoint of heat resistance and a mechanical characteristic improvement.

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, and the like. In order to promote crosslinking more efficiently, it is preferable to use electron rays and γ rays. Moreover, as irradiation dose of ionizing radiation, it is preferable that they are 10 kGy or more and 100 kGy or less, It is more preferable that they are 20 kGy or more and 80 kGy or less, It is still more preferable that they are 30 kGy or more and 70 kGy or less. By irradiating an ionizing radiation with the irradiation dose of this range, crosslinking fully advances and it can provide the outstanding heat resistance to a 5th flame-retardant laminated body. Irradiation time is not specifically limited, What is necessary is just to perform the time when the crosslinking reaction of this laminated body is fully completed.

At this time, it is important that the gel fraction of a laminated body is 15 mass% or more and 55 mass% or less, It is more preferable that they are 20 mass% or more and 40 mass% or less, It is further more preferable that they are 25 mass% or more and 45 mass% or less. If the gel fraction is less than 15 mass%, sufficient heat resistance imparting effect is not obtained. If the gel fraction is more than 55 mass%, the appearance and mechanical strength may be inhibited by excessive crosslinking.

<Use>

Since the fifth flame retardant laminate has excellent flame retardancy, heat resistance, and mechanical properties, the fifth flame retardant laminate can be used for applications such as electrical insulation materials, membrane switch circuit printing substrates, copier inner members, planar heating element substrates, and 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) The 0.25 g test piece cut out from the laminate is dissolved in 20 ml of chloroform at 23 ° C. for 5 hours.

(2) The insolubles are separated at a rotational speed of 11,400 rpm using a tabletop high speed centrifuge 3-18K manufactured by Sigma Laborzentrifugen GmbH.

(3) After drying the insoluble matter obtained by said (2) and removing components (for example, melamine and an inorganic substance) other than a resin component, a gel fraction is computed by the following formula | equation.

Gel fraction (mass%) = A / B × 100

A: The mass of the insoluble matter of the resin component after subtracting the mass of components (for example, melamine and an inorganic substance) other than the resin component obtained by said (3).

B: The theoretical mass of the resin component which subtracted the mass of components (for example, melamine and inorganic substance) other than the resin component which occupies in a laminated body.

In addition, when the compounding quantity of melamine is not known beforehand, what is necessary is just to calculate a melamine addition amount by the intensity | strength of the peak (815 cm <^-1> ) derived from the triazine ring of melamine by IR (infrared absorption analysis) measurement. In addition, when the compounding quantity of an inorganic substance is not known previously, what is necessary is just to calculate the addition amount of an inorganic substance from the sum total of an inorganic element by elemental analysis.

[Sixth flame retardant laminate]

Next, the flame retardant laminate according to the sixth embodiment (hereinafter referred to as "sixth flame retardant laminate") will be described.

The sixth flame-retardant laminate has a layer made of a resin composition (a) containing, as a main component, a mixture of polyester-based resin (6-A), melamine, and a carbonization accelerator having a glass transition temperature of 30 ° C. or lower, and on the A layer. Lamination which has B layer which consists of resin composition (b) which has polyester-based resin (6-B) whose glass transition temperature is 50-120 degreeC, and crystal calorific value ((DELTA) Hm) is 40-100 J / g. As a sieve, the proportion of melamine in the resin composition (a) constituting the A layer is 20 to 80 mass%, and the proportion of the carbonization accelerator in the resin composition (a) is 1 to 30 mass%. It is a laminate for cables.

This 6th flame-retardant laminated body can express a higher flame retardance by mix | blending melamine and a carbonization promoter with specific polyester resin which comprises an contact bonding layer (A layer). Moreover, since it does not contain a halogen type compound and a phosphorus compound, the material excellent in safety which does not cause a problem, such as environmental pollution, can be provided.

Since melamine generates a nonflammable gas at the time of combustion, not only can the flame retardant adhesive layer be burned, but also the outer layer (B layer) which does not contain a flame retardant can be flame retarded, thereby significantly increasing the flame retardancy of the entire laminate. Can be. Furthermore, by blending melamine and a carbonization accelerator, carbonization of the resin proceeds rapidly during combustion, and a laminate for wiring cables that can satisfy the UL1581VW-1 standard can be provided.

On the other hand, a 6th flame-retardant laminated body is polyester-based resin (6-B) on the A layer which consists of a resin composition (a) which has a mixture of polyester-based resin (6-A), melamine, and a carbonization accelerator as a main component. It is a laminated body provided with the B layer which consists of a resin composition (b) which has as a main component.

Here, "on A layer" includes the case of laminating the B layer via another layer on the A layer, in addition to the case of laminating the B layer directly on the A layer.

It will be described in detail below.

<A layer>

In the sixth flame retardant laminate, the layer A has a role of an adhesive layer, and the layer A is composed of a resin composition (a) composed mainly of a mixture composed of a polyester resin (6-A), melamine and a carbonization accelerator. It is a layer made up.

(Polyester Resin (6-A))

It is important that polyester-type resin (6-A) is resin whose glass transition temperature is 30 degrees C or less. If the glass transition temperature of polyester-type resin (6-A) is 30 degrees C or less, it can be set as the laminated body which has the outstanding mechanical characteristic in the wide range from low temperature to normal use temperature.

From this point of view, the glass transition temperature of the polyester resin (6-A) is preferably -80 ° C or higher, more preferably -70 ° C or higher, 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.

It is preferable that polyester-based resin (6-A) is resin whose crystal melting heat amount ((DELTA) Hm) is 5-30 J / g. When the heat of fusion of crystals (ΔHm) of the polyester-based resin (6-A) is 5 to 30 J / g, the laminate may have a sufficient adhesiveness and heat resistance at the time of molding, secondary processing, and use.

From this viewpoint, it is preferable that the amount of crystal melting heat (ΔHm) of the polyester resin (6-A) is 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 more preferable that it is 20 J / g or less.

As polyester-based resin (6-A), 1 type, or 2 or more types of mixed resin can be used among aliphatic polyester, aromatic aliphatic polyester, and polyester type hot melt adhesive. That is, single resin may be sufficient as polyester-type resin (6-A), and the mixture of two or more types of resin may be sufficient as it.

Examples of the aliphatic polyester used as the polyester resin (6-A) include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid, and 1,4. 1 or 2 or more aliphatic dicarboxylic acids in 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, neopentylglycol, 1,5-pentanediol , 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A and tetra The copolymer polyester which consists of 1 type, or 2 or more types of polyhydric alcohols in bromobisphenol A-bis (2-hydroxyethyl ether) is mentioned.

More specifically, a copolymer of succinic acid and 1,4-butanediol ("GSPla" AZ series by Mitsubishi Chemical Corporation, "Bionore" # 1000 series by Showa Polymer Corporation), succinic acid, 1,4-butanediol and adipic And aliphatic polyesters such as polybutylene succinate adipate copolymers ("GSPla" AD series manufactured by Mitsubishi Chemical Corporation, "Bionore" # 3000 series manufactured by Showa Polymer Corporation), which are copolymers of acids.

As aromatic aliphatic polyester used as polyester-type resin (6-A), terephthalic acid, isophthalic acid, 2-chloro terephthalic acid, 2,5- dichloro terephthalic acid, 2-methyl terephthalic acid, 4,4-stilbendicarboxylic acid Acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthraceneca One or two of leric acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid and ethylene-bis-p-benzoic acid One or more of the above aromatic dicarboxylic acids and succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, or Two or more aliphatic dicarboxylic acids, diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-prop Pandiol, trans-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentylglycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A and tetrabro The copolyester which consists of 1 type, or 2 or more types of polyhydric alcohols in mobisphenol A-bis (2-hydroxyethyl ether) is mentioned.

More specifically, the polybutylene adipate-terephthalate copolymer obtained by superposing | polymerizing adipic acid, 1, 4- butanediol, and terephthalic acid (the "Ecofurex" series by BASF Corporation, "Eastar Bio" by Eastman Chemicals Corporation) Aromatic aliphatic polyesters, such as the series), are mentioned.

Among the above, at least one polyhydric carboxylic acid component selected from succinic acid, adipic acid, terephthalic acid and isophthalic acid, and 1,4-butanediol, 1,6-hexanediol, ethylene glycol and polytetramethylene ether glycol Co-polyester containing at least 1 type of polyhydric-alcohol component is preferable as polyester resin (6-A).

It is preferable that the mass mean molecular weights of these aliphatic polyester and aromatic aliphatic polyester are 50,000-400,000. If the mass average molecular weight of these polyesters is 50,000 or more, the problem that a laminated body will be damaged by lack of flame retardance or a lack of mechanical strength does not arise. Moreover, if the mass mean molecular weight is 400,000 or less, the problem of molding failure due to too high a viscosity of the resin does not occur.

From this point of view, 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 more preferable that it is 250,000 or less.

In addition, a mass average molecular weight can be measured by the following method. The same applies to other resins. Using gel permeation chromatography, the solvent can be measured 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, and a solvent temperature of 40 ° C. to calculate the mass average molecular weight in terms of polystyrene. have. The mass average molecular weight of the standard polystyrene used at this time is 2,000,000, 430,000, 110,000, 35,000, 10,000, 4,000, 600.

The polyester-based hot melt resin used as the polyester-based resin (6-A) is the same as the polyester-based hot melt adhesive used for the polyester-based resin (5-A) of the fifth flame retardant laminate.

(Melamine)

Melamine is the same as the melamine used for a 1st flame-retardant resin composition, and the same effect can be acquired. In addition, similar to the first flame retardant resin composition, melamine and other flame retardants or flame retardant aids may be used in combination within a range that does not impair the effect of the fifth flame retardant laminate.

(Carbonation accelerator)

As a carbonization promoter, it is an inorganic substance or organic substance which can accelerate carbonization of resin at the time of combustion, As a specific example, Polyhydric alcohols, such as pentaerythritol, dipentaerythritol, and tripentaerythritol, guanidine sulfamate, phosphoric acid Guanidine compounds such as guanidine, sulfuric acid compounds such as melamine sulfate and ammonium sulfate, nitrate compounds such as melamine nitrate and ammonium nitrate, phenoxy resins having hydroxyl groups, silicone oils such as silicone oil, silicone rubber and silicone resin, melamine cyanurate And metal hydroxides such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide, calcium aluminate hydrate, tin oxide hydrate, and talc, mica, zinc borate, zinc oxide, magnesium oxide, and the like. Among these, in particular, by using a phenoxy resin, in addition to the 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 for use in the sixth flame retardant laminate include metal hydroxides such as aluminum hydroxide, ammonium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide and iron hydroxide, polyvinyl alcohol, phenoxy resin, urethane resin, and cellulose. And organic substances such as ether, lignin, sucrose, chitosan, pentaerythritol, dipentaerythritol, and tripentaerythritol.

(Phenoxy resin)

The phenoxy resin is the same as the phenoxy resin used for the second flame retardant resin composition, and the same effect can be obtained.

<Mixing 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 mass%. Sufficient flame retardance can be obtained as the compounding ratio of melamine which occupies in the resin composition (a) which comprises A layer is 20 mass% or more. 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 are not impaired.

From such a viewpoint, it is preferable that the mixture ratio of the melamine which occupies in the resin composition (a) which comprises A layer is 30 mass% or more, and it is still more preferable that it is 40 mass% or more especially. Moreover, it is preferable that it is 70 mass% or less, and especially it is more preferable that it is 60 mass% or less.

It is important that the compounding ratio of the carbonization accelerator which occupies in the resin composition (a) which comprises A layer is 1-30 mass%. Sufficient carbonization promoting effect can be acquired as the compounding ratio of the carbonization accelerator which occupies in the resin composition (a) which comprises A layer is 1 mass% or more. 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 are not impaired.

From such a viewpoint, it is preferable that the compounding ratio of melamine which occupies in the resin composition (a) which comprises A layer is 1 mass% or more, and it is still more preferable that it is 5 mass% or more especially. Moreover, it is preferable that it is 30 mass% or less, and it is more preferable especially that it is 20 mass% or less.

<B layer>

B layer is a layer which consists of resin composition (b) which has polyester resin (6-B) as a main component.

(Polyester Resin (6-B))

As polyester-based resin (6-B), it is important to use polyester-type resin whose glass transition temperature is 50-120 degreeC, and crystal heat of fusion ((DELTA) Hm) is 40-100 J / g. By satisfying this condition, a laminate having excellent heat resistance can be provided.

It is important that the glass transition temperature of polyester-type resin (6-B) is 50-120 degreeC as mentioned above. If the glass transition temperature of polyester-type resin (6-B) is 50-120 degreeC, it can be set as the laminated body which has the outstanding moldability and the outstanding heat resistance at the time of use.

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 especially it is more preferable that it is 100 degrees C or less.

It is important that the amount of crystal melting heat (ΔHm) of the polyester resin (6-B) is 40 to 100 J / g as described above. If the amount of heat of fusion (ΔHm) of the polyester resin (6-B) is 40 to 100 J / g, problems such as deformation during secondary processing may not occur.

From this viewpoint, it is preferable that the amount of crystal melting heat (ΔHm) of the polyester resin (6-B) is 45 J / g or more, and more preferably 50 J / g or more. Moreover, it is preferable that it is 90 J / g or less, and especially it is more preferable that it is 80 J / g or less.

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

At this time, as a polyhydric carboxylic acid component used for an aliphatic polyester or an aromatic polyester, for example, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4- Stilbendicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl Methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid, ethylene-bis-p-benzoic acid, etc. Aliphatic dicarboxylic acids such as aromatic dicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid A carboxylic acid component can be mentioned. These polyhydric carboxylic acid components can be used individually by 1 type or in mixture of 2 or more types.

As the polyhydric alcohol component, for example, 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, neopentylglycol, 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-hydr Oxyethyl ether). These polyhydric alcohol components can be used individually by 1 type or in mixture of 2 or more types.

As a specific example of the polyester-type resin comprised by the said polyhydric carboxylic acid component and a polyhydric alcohol component, For example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, Polybutylene naphthalate, polyethylene terephthalate, isophthalate, etc. are mentioned. Among them, it is particularly preferable to use polyethylene terephthalate and polybutylene terephthalate in terms of heat resistance.

It is preferable that the mass mean molecular weights of polyester-type resin (6-B) are 30,000-80,000. If the mass average molecular weight of polyester-type resin (6-B) is 30,000 or more, suitable resin cohesion force will be obtained and it can suppress that the elongation of a laminated body is insufficient or embrittled. On the other hand, if it is 80,000 or less, melt viscosity can be reduced and it is preferable from a viewpoint of manufacture and productivity improvement.

From such a viewpoint, the mass average molecular weight of the polyester resin (6-B) is particularly preferably 35,000 or more, more preferably 40,000 or more. Moreover, it is especially preferable that it is 75,000 or less, and especially it is more preferable that it is 70,000 or less.

B layer may be comprised by the stretched film, In that case, it is preferable that it is comprised by the biaxially stretched film.

&Lt; Other components >

In a 6th flame-retardant laminated body, you may mix | blend a carbodiimide compound with the resin composition (a) which comprises A layer and the resin composition (b) which comprises B layer in order to provide hydrolysis resistance. However, it does not need to mix.

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

As a compounding quantity of a carbodiimide compound, it is preferable to mix | blend 0.5-10 mass parts with respect to 100 mass parts of polyester resins (6-A) or 100 mass parts of polyester resins (6-B), and 1-5 It is more preferable to mix | blend a mass part. When it is less than such a range, the effect of providing durability is low, and when it exceeds this range, soft nitriding of a resin composition may arise, and heat resistance may be impaired.

To the A layer and the B layer constituting the sixth flame retardant laminate, additives for imparting functions, different resins, and the like may be added within a range that does not impair the effect of the sixth flame retardant laminate. Examples of the additive for imparting the function include a conductive agent, a flame retardant, a plasticizer, a lubricant, an antioxidant, an ultraviolet absorber, a pigment, and other fillers. Moreover, polyolefin resin, styrene resin, polyolefin resin, acrylic resin, polycarbonate resin, polyamide resin, etc. are mentioned as different resin.

<Layer thickness>

It is preferable that the layer thickness ratio of A layer with respect to the total layer thickness of a 6th flame-retardant laminated body is 20 to 70%. Sufficient flame retardance can be provided to a 6th flame-retardant laminated body by making the layer thickness ratio of A layer into 20% or more. On the other hand, sufficient mechanical characteristics can be provided to a 6th flame-retardant laminated body by making the layer thickness ratio of A layer into 70% or less.

From this point of view, the layer thickness ratio of the A layer to the total layer thickness of the sixth flame retardant laminate is particularly preferably 25% or more, more preferably 30% or more. Moreover, it is especially preferable that it is 60% or less, and it is still more preferable that it is 50% or less especially.

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

In addition, the sixth flame retardant laminate may include layers other than the A layer and the B layer. For example, another layer may be interposed between A-layer and B-layer, and the other layer may be provided in the outer side (opposite side to A-layer) of B-layer.

The thickness of the 6th flame-retardant laminated body is not specifically limited, It can adjust to the thickness according to each use, such as a film, a sheet, a panel.

<Flammability>

The sixth flame retardant laminate has very excellent flame retardancy and can satisfy UL1581VW-1, which is one index for evaluating flame retardancy. That is, the sixth flame-retardant laminate comprises a polyester-based resin (A) that satisfies certain conditions, a melamine and a carbonization accelerator as a main component, and forms a layer A, and a polyester-based resin (6-B) that satisfies certain conditions. By constituting the B layer 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.

<Use>

The sixth flame retardant laminate can obtain flame retardancy, particularly flame retardancy satisfying the UL1581VW-1 standard, and can be suitably used as, for example, a coated resin film covering a wiring cable. That is, a wiring cable can be manufactured by using two sixth flame retardant laminates, arranging a metal conductor between these A layers, and bonding the two laminates together.

In particular, the sixth flame retardant laminate is particularly suitable for flat cables because not only can excellent flame retardancy be obtained as described above, but also excellent flexibility and excellent heat resistance.

[Description 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 disturb the function of the main component, unless otherwise specified. Although it does not specifically specify the content rate of the said main component, The component (the total amount of these components, when two or more components are a main component) is 60 mass% or more in this composition, especially 70 mass% or more, especially 90 mass% or more (100%) It is preferable to occupy. For example, it is preferable that the mixture in a resin composition (a) occupies 60 mass% or more, especially 70 mass% or more, especially 90 mass% or more (including 100%) in a resin composition (a).

In addition, in this specification, when it describes as "X-Y" (X and Y are arbitrary numbers), it is a meaning of "X or more and Y or less", unless it mentions specially, "It is larger than X preferably" or " Preferably it is smaller than Y ".

In addition, when describing as "X or more" (X is arbitrary number) or "Y or less" (Y is arbitrary number), the intention of the meaning of "it is preferable that it is larger than X" or "it is preferable that it is less than Y" Also includes.

In general, "film" refers to a thin, flat product having a very small thickness compared to its length and width, and having a maximum thickness arbitrarily defined. Usually, the film is supplied in a roll form (Japanese Industrial Standard JIS K 6900). A sheet "is thin in the definition in JIS, and refers to a product whose thickness is small and flat compared to the length and width. However, the boundary between the sheet and the film is not clear, and in the present invention, since it is not necessary to distinguish both, in the present invention, even when referred to as "film", "sheet" is assumed to be "sheet". Even if called, it shall include a "film."

In addition, "wiring cable" means having the structure which coat | covers a metal conductor with a resin film, for example, the flat cable provided with the structure which arrange | positions two or more metal conductors and coats these with a resin film is typical. Yes.

"Glass transition temperature" and "crystal melting heat quantity" of polyester-type resin in this invention are the values measured as follows. Also in the Example and comparative example mentioned later, it measured by the method demonstrated next unless there is particular notice.

(1) A polyester resin is made into a flaky shape of about 10 mg of 5 mm in diameter to be a test sample.

(2) The test sample obtained in the above (1) was held by a differential scanning calorimeter (Perkin Elmer DSC-7) based on JIS-K 7121 for 2 minutes at 200 ° C, and then at a rate of 10 ° C / min. To -40 ° C. Subsequently, temperature rising measurement is performed at -10 degreeC / min from -40 degreeC to 200 degreeC. In addition, a series of measurements are performed in nitrogen atmosphere.

(3) The glass transition temperature and the amount of crystal melting heat are read from the thermogram obtained by the above measurement (2).

Example

Hereinafter, Examples and Comparative Examples corresponding to each of the above-described first and second embodiments (flame retardant polyester resin composition) and third to sixth embodiments (flame retardant laminate) will be described.

However, the scope of the present invention is not limited to the following example.

[Examples and Comparative Examples of First Embodiment]

First, the Example and comparative example which concern on 1st Embodiment is demonstrated.

(1) flame retardant

When thickness is 200 micrometers or less, the evaluation sample of length 200mm x width 50mm, and when thickness exceeds 200 micrometers, evaluation of length 127mm x width 13mm (thickness differs according to each test piece) Test samples, based on the sequence of the safety standard UL94 thin material vertical burning test (if the sample thickness is 200 μm or less), and UL94 vertical burning test (if the sample thickness is more than 200 μm) from Underwriters Laboratories. The five-time combustion test was conducted, the combustion mode (particularly, the presence or absence of a drop during combustion) was observed, and the combustion time (total number of five test times of the test) was measured.

In the UL94 vertical combustion test, for a sample having a thickness of 200 μm or less, it is determined based on the criteria of UL94VTM to determine whether the standards of VTM-0, 1, and 2 are satisfied, and not satisfying VTM-2. It evaluated externally and the thing which satisfy | fills VTM-0 was evaluated as a pass product. For samples having a thickness of more than 200 µm, it is determined whether or not the standards of VTM-0, 1 and 2 are satisfied based on the UL94V criterion. And satisfying VTM-0 were evaluated as passing products.

(2) tensile strength, tensile elongation

Tensile breaking strength and tensile breaking elongation were measured based on JIS C 2318 using the sample for evaluation 200 mm in length x 20 mm in width. The strength and elongation at break were measured and the average value at n = 5 was obtained. It measured by the atmospheric temperature of 23 degreeC, 50% of the relative humidity, 200 mm / min of tensile velocity, and 100 mm of clamp space | intervals, the intensity | strength and elongation at break were measured, and the average value in n = 5 was calculated | required.

Tensile strength was 10 Mpa or more, and tensile elongation evaluated 10% or more as the pass.

(3) crystal melting calories (ΔHm)

Based on JIS K 7121, the heat | fever which melt | dissolved crystal | crystallization ((DELTA) Hm) of polyester-type resin was measured using the Perkin Elmer company DSC-7 about the sample scraped off about 10 mg. The measurement procedure is shown below.

a. After heating up from 30 degreeC to 200 degreeC at a speed | rate of 500 degreeC / min, it hold | maintained at 200 degreeC for 2 minutes.

b. Next, temperature-fall measurement was performed from 200 degreeC to 30 degreeC at the speed of 10 degreeC / min.

c. Moreover, temperature rising measurement was performed from 30 degreeC to 200 degreeC at the speed of 10 degreeC / min.

C. The heat of fusion of crystals (ΔHm) was read from the thermogram obtained in the course of.

(4) Heat resistance

One side edge part of the evaluation sample of length 200mm x width 20mm was fixed, it hold | maintained perpendicularly in the baking test apparatus (DKS-5S made from Taisei Scientific regular make), and it heated at 140 degreeC for 1 hour. The external appearance of the sample after heating was observed visually, and it was determined that there was no remarkable change as compared with before heating, and that the shrinkage, wrinkles, remarkable deformation, etc. were generated as compared with before heating.

<Raw material>

Next, the raw material used by the Example-the comparative example, ie, polyester-based resin (A), polyester-based resin (B), and melamine is demonstrated.

[Polyester-Based Resin (A) -1]

Product Name: Toyo Spinning Company Manufacture Byron GM-443

Composition: polyhydric carboxylic acid component = 53 mol% of terephthalic acid, 38 mol% of isophthalic acid, 9 mol% of adipic acid, polyhydric alcohol component = 100 mol% of 1, 4- butanediol

Properties: Mass Average Molecular Weight = 47,000, Tg = 26 ℃, Tm = 145 ℃, ΔHm = 22.8 J / g

[Polyester-Based Resin (A) -2]

Product Name: Toyo Spun Yarn Byron GA-1300

Composition: polyhydric carboxylic acid component = 66 mol% of terephthalic acid, 10 mol% of isophthalic acid, 24 mol% of adipic acid, polyhydric alcohol component = 100 mol% of 1, 4- butanediol

Properties: Mass Average Molecular Weight = 50,000, Tg = -6 ℃, Tm = 167 ℃, ΔHm = 23.7 J / g

[Polyester-Based Resin (A) -3]

Product Name: Toyo Spun Yarn Byron GA-1310

Composition: polyhydric carboxylic acid component = 71 mol% of terephthalic acid, 29 mol% of isophthalic acid, polyhydric alcohol component = 100 mol% of 1, 4- butanediol

Properties: Mass Average Molecular Weight = 56,000, Tg = 27 ℃, Tm = 179 ℃, ΔHm = 24.5 J / g

[Polyester-Based Resin (B) -1]

Product Name: Toyo Spinning Company Byron 30P

Composition: polyhydric carboxylic acid component = 54 mol% of terephthalic acid, 46 mol% of sebacic acid, polyhydric alcohol component = 82 mol% of 1,4-butanediol, ethylene glycol = 18 mol%

Properties: Mass Average Molecular Weight = 96,000, Tg = -28 ℃, Tm = 125 ℃, ΔHm = 2.0 J / g

[Polyester-Based Resin (B) -2]

Product Name: Toyo Spinning Company Manufacture Byron GM-913

Composition: polyhydric carboxylic acid component = 66 mol% of terephthalic acid, 34 mol% of isophthalic acid, polyhydric alcohol component = 82 mol% of 1, 4- butanediol, 18 mol% of polytetramethylene ether glycol

Properties: Mass Average Molecular Weight = 100,000, Tg = -70 ℃, Tm = 126 ℃, ΔHm = 10.2 J / g

[Melamine]

Fine powder melamine manufactured by Nissan Chemical Industries, Ltd. (average particle size 5 µm, no surface treatment)

(Example 1-1)

After dry blending the polyester-based resin (A) -1 and the finely divided melamine with a mixed mass ratio of 80:20, kneading at 200 ° C using a 40 mmφ coaxial twin screw extruder, extruding from the T die, and then It quenched with the casting roll of 40 degreeC, and the sheet | seat of 100 micrometers in thickness was produced. 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 mixed mass ratio of the polyester resin (A) -1 and the finely divided melamine was 70:30. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to 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 mixed mass ratio of the polyester resin (A) -1 and the finely divided melamine was 50:50. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Examples 1-4)

After blending polyester-based resin (A) -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 performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Example 1-5)

After blending polyester-based resin (A) -3 and finely divided melamine in a mixing mass ratio of 70:30, the sheet | seat of 100 micrometers in thickness was produced by the same method as Example 1-1. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Example 1-6)

After blending polyester-based resin (A) -2, polyester-based resin (B) -1 and finely divided melamine in a mixing mass ratio of 50:20:30, a sheet having a thickness of 100 µm was prepared in the same manner as in Example 1-1. Prepared. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Example 1-7)

After blending polyester-based resin (A) -2, polyester-based resin (B) -1 and finely divided melamine in a mixing mass ratio of 40:30:30, a sheet having a thickness of 100 µm was prepared in the same manner as in Example 1-1. Prepared. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Examples 1-8)

After blending polyester-based resin (A) -2, polyester-based resin (B) -1 and finely divided melamine in a mixing mass ratio of 30:40:30, a sheet having a thickness of 100 µm was prepared in the same manner as in Example 1-1. Prepared. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Examples 1-9)

After blending polyester-based resin (A) -2, polyester-based resin (B) -2 and finely divided melamine in a mixing mass ratio of 40:30:30, a sheet having a thickness of 100 µm was prepared in the same manner as in Example 1-1. Prepared. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Comparative Example 1-1)

After blending polyester-based resin (A) -1 and finely divided melamine in 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 performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Comparative Example 1-2)

After blending polyester-based resin (A) -1 and finely divided melamine in 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 performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Comparative Example 1-3)

After blending polyester-based resin (B) -2 and finely divided melamine in 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 performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Comparative Example 1-4)

Instead of melamine, polyester resins (A) -1 and PHOSMEL-200 were blended at a mixing mass ratio of 70:30 using PHOSMEL-200 (polyphosphate melamine) manufactured by Nissan Chemical Industries, Ltd., and then the same as in Example 1-1. The sheet | seat of thickness 100micrometer was produced by the method. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Comparative Example 1-5)

Instead of melamine, polyester resins (A) -1 and MC-860 were blended in a mixed mass ratio of 70:30 using Nissan Chemical Industry Co., Ltd. MC-860 (melamine cyanurate), followed by Example 1-1 and In the same manner, a sheet having a thickness of 100 m was prepared. Table 1 shows the results of performing the same evaluation as in Example 1-1 with respect to the obtained sheet.

(Review)

In the flame-retardant polyester-based resin composition obtained by mixing polyester-based resin (A) and melamine whose glass transition temperature (Tg) is -20 degreeC-40 degreeC, and crystal melting temperature (Tm) is 140 degreeC-190 degreeC In the flame retardant polyester resin composition, the proportion of melamine in the range of 20 to 60% by mass was found to be acceptable for evaluation of flame retardancy, tensile strength, tensile elongation, and heat resistance.

In addition, flame retardation can be achieved by blending melamine with the polyester resin (A), while melamine derivatives such as melamine cyanurate and melamine polyphosphate cannot flame retard the specific polyester resin (A). The result was obtained.

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 turned out that it is preferable that the ratio of melamine is 20-60 mass% of a flame-retardant polyester resin composition.

Moreover, polyester-based resin (A) and poly are polyester-based resin (B) whose glass transition temperature (Tg) is -100 degreeC or more and less than -20 degreeC, and crystal melting temperature (Tm) is 100 degreeC or more and less than 140 degreeC. By blending so that the mass ratio of ester resin (B) is 90: 10-10: 70, it turns out that pass evaluation of all flame retardance, tensile strength, tensile elongation, and heat resistance can be obtained, and especially tensile elongation can be improved. there was.

[Examples and Comparative Examples of Second Embodiment]

Next, the Example and comparative example which concern on 2nd Embodiment is demonstrated.

(1) flame retardant

When thickness is 200 micrometers or less, the sample for evaluation of length 200mm x width 50mm (thickness changes with each test piece), and when thickness exceeds 200micrometer, length 127mm x width 13mm (thickness Uses a sample for evaluation of different specimens), the safety standard UL94 thin material vertical combustion test (if the sample thickness is 200 μm or less) from Underwriters Laboratories, and the UL94 vertical combustion test (the sample thickness is 200 μm). On the basis of the procedure in the case of exceeding, a 5-time combustion test is conducted to observe the combustion mode (particularly, the presence or absence of a load in the combustion) and to measure the combustion time (5 total combustion times). It was.

In the UL94 vertical combustion test, for a sample having a thickness of 200 μm or less, it is determined based on the criteria of UL94VTM to determine whether the standards of VTM-0, 1, and 2 are satisfied, and not satisfying VTM-2. It evaluated externally and the thing which satisfy | fills VTM-0 was evaluated as a pass product. For samples with a thickness of more than 200 μm, it is judged whether or not the standards of VTM-0, 1 and 2 are satisfied based on the UL94V criterion. And satisfying VTM-0 were evaluated as passing products.

(2) tensile strength, tensile elongation

Tensile breaking strength and tensile breaking elongation were measured based on JIS C 2318 using the sample for evaluation of length 200mm x width 20mm (thickness differs with each test piece). The strength and elongation at break were measured and the average value at n = 5 was obtained. It measured by the atmospheric temperature of 23 degreeC, 50% of the relative humidity, 200 mm / min of tensile velocity, and 100 mm of clamp space | intervals, the intensity | strength and elongation at break were measured, and the average value in n = 5 was calculated | required.

Tensile strength was 10 Mpa or more, and tensile elongation evaluated 10% or more as the pass.

(3) stress relaxation characteristics

Using the sample for evaluation of length 200mm x width 20mm (thickness differs with each test piece), based on JISC2318, atmospheric temperature 23 degreeC, relative humidity 50%, tensile rate 200mm / min, From the stress (I) when 10% tension | tensile | strengthening based on a clamp space | interval at 100 mm of clamp spacings, and the stress (II) after hold | maintaining for 5 minutes in that state, {(I)-(II) / (I) } The stress relaxation ratio was measured by the formula of x 100 (%).

The stress relaxation ratio evaluated 50% or more as the pass. In addition, when a 10% tension was performed, the fracture | rupture of the sample evaluated evaluation as impossible.

(4) crystal melting calories

Measurement and evaluation were performed similarly to the Example concerning 1st Embodiment.

<Raw material>

Next, the raw material used by the Example-the comparative example, ie, polyester-based resin (A), melamine, and polyester-based resin (B) is demonstrated.

[Polyester-Based Resin (A) -1]

Product Name: Toyo Spun Yarn Byron GA-1300

Composition: polyhydric carboxylic acid component = 66 mol% of terephthalic acid, 10 mol% of isophthalic acid, 24 mol% of adipic acid, polyhydric alcohol component = 100 mol% of 1, 4- butanediol

Properties: Mass Average Molecular Weight = 50,000, Tg = -6 ℃, Tm = 167 ℃, ΔHm = 23.7 J / g

[Polyester-Based Resin (A) -2]

Product Name: Toyo Spun Yarn Byron GA-1310

Composition: polyhydric carboxylic acid component = 71 mol% of terephthalic acid, 29 mol% of isophthalic acid, polyhydric alcohol component = 100 mol% of 1, 4- butanediol

Properties: Mass Average Molecular Weight = 56,000, Tg = 27 ℃, Tm = 179 ℃, ΔHm = 24.5 J / g

[Polyester-Based Resin (A) -3]

Product Name: Toyo Spinning Company Byron 30P

Composition: polyhydric carboxylic acid component = 54 mol% of terephthalic acid, 46 mol% of sebacic acid, polyhydric alcohol component = 82 mol% of 1,4-butanediol, ethylene glycol = 18 mol%

Properties: Mass Average Molecular Weight = 96,000, Tg = -28 ℃, Tm = 125 ℃, ΔHm = 2.0 J / g

[Polyester-Based Resin (A) -4]

Product Name: Foriesta SP160 manufactured by Nippon Synthetic Chemical Co., Ltd.

Composition: polyhydric carboxylic acid component = 62 mol% of terephthalic acid, 19 mol% of adipic acid, 19 mol% of sebacic acid, polyhydric alcohol component = 100 mol% of 1, 4- butanediol,

Properties: Mass Average Molecular Weight = 82,000, Tg = -20 ℃, Tm = 150 ℃, ΔHm = 26.0 J / g

[Polyester-Based Resin (A) -5]

Product Name: Toyo Spinning Company Manufacture Byron GM-470

Composition: Polyhydric carboxylic acid component = 86 mol% of terephthalic acid, 14 mol% of adipic acid, polyhydric alcohol component = 87 mol% of 1, 4- butanediol, and 13 mol% of 1, 6- heptanediol

Properties: Mass Average Molecular Weight = 58,000, Tg = 20 ℃, Tm = 185 ℃, ΔHm = 27.0 J / g

[Polyester-Based Resin (A) -6]

Product Name: Toyo Spun Yarn Perufuren P40B

Composition: polyhydric carboxylic acid component = terephthalic acid 100 mol%, polyhydric alcohol component = 1,4-butanediol 73 mol%, polytetramethylene ether glycol 27 mol%

Properties: Mass Average Molecular Weight = 148,000, Tg = -70 ℃, Tm = 180 ℃, ΔHm = 2.3 J / g

Melamine (B) -1

Fine powder melamine manufactured by Nissan Chemical Industries, Ltd. (average particle size 5 µm, 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: E1256 manufactured by Japan Epoxy Resin Co., Ltd.

Composition: bisphenol A = 100 mol%

(Example 2-1)

After dry blending (A) -1, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 55: 20: 15: 5, a 40 mm diameter coaxial twin screw extruder was used. After kneading at 200 ° C., it was extruded from a T die and then quenched with a casting roll of about 40 ° C. to prepare 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)

The same method as in Example 2-1, except that the mixed mass ratio of the polyester resins (A) -1, (A) -3, (B) -1, and (C) -1 was set to 45: 20: 30: 5. To prepare a sheet having a thickness of 100 μm. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-3)

The same method as in Example 2-1, except that the mixed mass ratio of the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 was set to 15: 20: 55: 5. To prepare a sheet having a thickness of 100 μm. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-4)

Example 2-1 after dry blending polyester-based resin (A) -2, (A) -3, (B) -1, and (C) -1 in the ratio of the mixture mass ratio 45: 20: 30: 5 In the same manner as in the sheet of 100 ㎛ thickness was prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-5)

After dry blending (A) -3, (B) -1 and (C) -1 in the ratio of the mixing mass ratio 65: 30: 5, the sheet | seat of 100 micrometers in thickness was produced by the method similar to Example 2-1. . The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-6)

The polyester resins (A) -1, (B) -1 and (C) -1 were dry blended in a ratio of a mixed mass ratio of 65: 30: 5, and then 100 µm thick in the same manner as in Example 2-1. Sheets were prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-7)

The polyester resins (A) -4, (B) -1 and (C) -1 were dry blended at a ratio of the mixed mass ratio of 65: 30: 5, and then 100 µm thick in the same manner as in Example 2-1. Sheets were prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-8)

The polyester resins (A) -5, (B) -1 and (C) -1 were dry blended at a ratio of the mixed mass ratio of 65: 30: 5, and then 100 µm thick in the same manner as in Example 2-1. Sheets were prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-9)

Example 2-1 after dry blending polyester-based resin (A) -1, (A) -3, (B) -1, and (C) -1 in the ratio of the mixing mass ratio 48: 20: 30: 2 In the same manner as in the sheet of 100 ㎛ thickness was prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-10)

Example 2-1 after dry blending polyester-based resin (A) -1, (A) -3, (B) -1, and (C) -1 in the ratio of 40: 20: 30: 10 In the same manner as in the sheet of 100 ㎛ thickness was prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-11)

Example 2-1 after polyester-based resins (A) -1, (A) -3, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 30: 20: 30: 20 In the same manner as in the sheet of 100 ㎛ thickness was prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-12)

Example 2-1 after dry blending polyester-based resin (A) -1, (A) -3, (B) -1, and (C) -2 in the ratio of 40: 20: 30: 10 In the same manner as in the sheet of 100 ㎛ thickness was prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Example 2-13)

In the same manner as in Example 2-2, the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 were blended in a mixed mass ratio of 45: 20: 30: 5 It compounded at 190 degreeC using the Mitsubishi hollow 40 mm diameter small coaxial twin screw extruder, and was made into the pellet form. The obtained pellet was injection-molded the board | plate material of length 250mm x width 200mm x thickness 1mm using the TOSHIBA machine make injection molding machine IS50E (screw diameter 25mm). Main molding conditions are as follows.

1) Temperature condition: cylinder temperature (190 ℃) mold temperature (30 ℃)

2) Injection condition: Injection pressure (115 MPa) Holding pressure (55 MPa)

3) Weighing condition: Screw rotation speed (65 rpm) Back pressure (15 MPa)

The result of having evaluated the sample for evaluation from the obtained molded article and performing the same evaluation as Example 2-1 is shown in Table 2.

(Comparative Example 2-1)

The polyester resins (A) -1, (A) -3 and (B) -1 were dry blended at a ratio of the mixed mass ratio of 50:20:30, and then 100 µm thick in the same manner as in Example 2-1. Sheets were prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Comparative Example 2-2)

Example 2-1 after polyester-based resins (A) -1, (A) -3, (B) -1 and (C) -1 were dry blended at a ratio of a mixed mass ratio of 70: 20: 5: 5 In the same manner as in the sheet of 100 ㎛ thickness was prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Comparative Example 2-3)

The polyester resins (A) -1, (B) -1 and (C) -1 were dry blended in a ratio of the mixed mass ratio of 35:25:40, and then 100 µm thick in the same manner as in Example 2-1. Sheets were prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Comparative Example 2-4)

The polyester resins (A) -1, (B) -1 and (C) -1 were dry blended at a ratio of the mixed mass ratio of 25: 70: 5, and then 100 µm thick in the same manner as in Example 2-1. Sheets were prepared. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Comparative Example 2-5)

Instead of melamine, polyester resins (A) -1, (A) -3, (C) -1 and MC-860 were mixed using a Nissan Chemical Industry Co., Ltd. MC-860 (melamine cyanurate) in a mass ratio of 45: After dry blending at a ratio of 20: 5: 30, a sheet having a thickness of 100 µm was prepared in the same manner as in Example 2-1. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Comparative Example 2-6)

Instead of melamine, (A) -1, (A) -3, (C) -1 and H42S were mixed by using H42S (a stearic acid treated aluminum hydroxide) manufactured by Showa Denko, at a mass ratio of 45: 20: 5: 30. After dry blending in proportion, a sheet having a thickness of 100 μm was produced in the same manner as in Example 2-1. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

(Comparative Example 2-7)

Instead of the polyester resin (A), (A) -6, (B) -1 and (C) -1 were mixed in a mass ratio of 65:25, using polyester resin (A) -6 (ferrufurene P40B). After dry blending at a ratio of 10, a sheet having a thickness of 100 µm was produced in the same manner as in Example 2-1. The result of having evaluated similarly to Example 2-1 about the obtained sheet | seat is shown in Table 2.

Polyester resin (A) containing 50-90 mol% of terephthalic acid as a polyhydric carboxylic acid component, and 70-100 mol% in total of 1, 4- butanediol, ethylene glycol, and diethylene glycol as a polyhydric alcohol component By using, it was found that excellent tensile strength, tensile elongation and stress relaxation characteristics can be obtained.

Especially, polyester resin which contains isophthalic acid in the ratio of 5 mol% or more and less than 30 mol% in a polyhydric carboxylic acid component, and contains ethylene glycol in the ratio of 0 mol% or more and less than 50 mol% in a polyhydric alcohol component. (a-1) and isophthalic acid are contained in the polyhydric carboxylic acid component in the ratio of 30 mol% or more and 50 mol% or less, and ethylene glycol is contained in the polyhydric alcohol component in the ratio of 50 mol% or more and 100 mol% or less By using the mixture of the polyester resin (a-2), it was found that more excellent tensile strength, tensile elongation and stress relaxation characteristics can be obtained.

By blending the phenoxy resin (C) with the polyester resin (A), it was confirmed that the stress relaxation characteristics of the polyester resin (A) can be improved, and further, the flame retardancy can be further improved. .

It is preferable that the ratio of a phenoxy resin (C) is 1-25 mass% of a flame-retardant polyester resin composition, It is more preferable that it is 2 mass% or more, Especially 5 mass% or more, Especially 20 mass% or less, The It turned out that it is more preferable that it is 10 mass% or less especially.

In addition, flame retardation can be achieved by blending melamine with the polyester resin (A), while melamine derivatives such as melamine cyanurate and melamine polyphosphate cannot flame retard the specific polyester resin (A). The result was obtained.

Although melamine is generally difficult to use as a flame retardant, it has been found that it can be used as a flame retardant for certain polyester resins. That is, from the result of Table 2, it turns out that it does not function as a flame retardant about polyester resin (A) -6, but functions as a flame retardant about polyester resin (A) -1-(A) -5. there was.

It is preferable that the ratio of melamine (B) is 10-60 mass% of a flame-retardant polyester-type resin composition, It is more preferable that it is especially 20 mass% or more, Especially 30 mass% or more, 50 mass% or less, Especially 40 It turned out that it is more preferable that it is mass% or less.

[Examples and Comparative Examples of Third Embodiment]

First, the Example and comparative example which concern on 3rd Embodiment is demonstrated.

The result shown in the following Example was evaluated by the following method.

(1) flame retardant

<UL94VTM>

Evaluation of the flame retardance of a flame retardant laminated body was evaluated by the UL94 vertical combustion test as follows. That is, using the evaluation sample of length 200mm x width 50mm (thickness differs with each test piece), based on the procedure of the safety standard UL94 vertical combustion test by Underwriters Laboratories, the test frequency 5 circuits of a combustion test are performed. Was carried out. UL94 vertical combustion test Based on the criterion of UL94VTM, the laminated body which satisfy | fills VTM-0 standard was made into the pass.

<Burn time>

In the UL94VTM test, the combustion time was evaluated in the following order.

First, it adjusted so that the burner flame length might be set to 20 mm +/- 1 mm, and made it contact for a predetermined time so that a flame might contact 10 mm +/- 1 mm to a test laminated body.

Next, the flame of the burner was dropped from the test laminate, and the combustion time of the test laminate was t1.

Next, after completion of the combustion time in the above, it was contacted in the same manner as described above for a predetermined time.

Next, the combustion time of the test laminated body after dropping the above contact salt was made into t2, and the lead-free combustion time of the test laminated body was made into t3.

In addition, the combustion time described in Table 3 and Table 4 describes the total time of t1, t2, and t3 of five sets of test laminates of the configurations described in Examples and Comparative Examples (VL94VTM test conformity).

(2) peel strength

Peeling strength measured the peeling strength between A-layer and B-layer using the tensile tester (Intesco Co., Ltd. material testing machine 201X with a thermostat). The measuring method was measured by the T-type peeling test (JIS K 6854-3 1999). The T-type peeling test was done at the atmospheric temperature of 23 degreeC, and peeling rate 10mm / min using the thing of 10 mm width of the sample for evaluation. Peeling strength set 4 N / 10 mm or more as the pass.

(3) tensile strength, tensile elongation

Tensile breaking strength and tensile breaking elongation were measured based on JIS C 2318 using the sample for evaluation of length 200mm x width 15mm (thickness differs with each test piece). The strength and elongation at break were measured and the average value at n = 5 was obtained. It measured by the atmospheric temperature of 23 degreeC, 50% of the relative humidity, 100 mm / min of tensile velocity, and 100 mm of clamp space | intervals, the strength and elongation at break were measured, and the average value in n = 5 was calculated | required. The tensile strength was 80 MPa or more and the tensile elongation was 50% or more.

(4) Heat resistance

The sample for evaluation of length 100mm x width 100mm (thickness differs with each test piece) is left to stand in the baking test apparatus (DKS-5S made from Taisei Scientific Instruments, Ltd.), and it is 15 minutes at 100 degreeC. Heated. The external appearance of the sample after the heating was observed visually, and the one with no change before the heating and with ○, shrinkage, wrinkles, deformation, etc. were generated.

<Production of Layer B>

`` B Layer-A ''

Using Novapex (registered trademark) (polyethylene terephthalate, IV: 0.65, ΔHm = 55 J / g) manufactured by Mitsubishi Chemical Corporation as a polyester resin, Novafex was first kneaded at 260 ° C. with a 40 mm diameter single screw extruder. It was extruded from the mold and then quenched with a casting roll of about 40 ° C. to prepare a amorphous sheet having a thickness of 225 μm. Subsequently, a sequential biaxial tenter manufactured by Mitsubishi Hollow Co., Ltd. was notified and stretched at a draw ratio of 3 times in MD (length direction) at 95 ° C, and then at 3 degrees in TD (horizontal direction) at 110 ° C. Stretched. Furthermore, after that, it heat-processed at 160 degreeC for 15 second, and obtained the 25-micrometer-thick biaxially stretched film.

`` B layer -B ''

After producing the 108-micrometer-thick amorphous sheet by the method and conditions similar to a polyester film (A), it extended | stretched by the same method and the conditions as a polyester film (A), and obtained the 12-micrometer-thick biaxially stretched film.

`` B Layer-C ''

Using coplyester6763 (polyethylene terephthalate glycol, glass transition temperature = 81 ° C, ΔHm = 0 J / g) as a polyester resin, coplyester6763 was kneaded at 260 ° C with a 40 mm diameter single screw extruder, and then detained from detention. It was extruded and then quenched with a casting roll of about 40 ° C. to prepare an amorphous sheet having a thickness of 25 μm.

(Example 3-1)

As a polyester-based resin (A), Toyo Spinning Co., Ltd. Byron GM-443 (terephthalic acid: 26.5 mol%, isophthalic acid: 19.8 mol%, adipic acid: 4.7 mol%, 1,4-butanediol: 50 mol%, glass transition temperature : 26 degreeC, fusion | melting calorie | heat amount ((DELTA) Hm): 22.8 J / g), Byron GM-443 and fine particle melamine are mixed using Nissan Chemical's fine particle melamine (average particle diameter: 5 micrometers) as a flame retardant. After dry blending at a mass ratio of 80:20, the mixture was kneaded at 200 ° C. using a 40 mm diameter coaxial twin screw extruder, extruded from the T die, and the B layer-A was pasted from the cast roll side, whereby the layer structure was A. The laminated body (A layer = 25 micrometers, B layer-A = 25 micrometer) of thickness 50 micrometers used as a layer / B layer was obtained. About the obtained laminated body, the result which evaluated flame retardance, peeling strength, tensile strength, and tensile elongation is shown in Table 3.

(Example 3-2)

The thickness of 50 µm (A layer = 25 µm, B layer -A = 25 µm) in the same manner as in Example 3-1, except that the mixed mass ratio of Byron GM-443 and microscopic melamine was 60:40 as the A layer. A laminate was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-3)

The thickness of 50 µm (A layer = 25 µm, B layer -A = 25 µm) in the same manner as in Example 3-1, except that the mixed mass ratio of Byron GM-443 and microscopic melamine was 40:60 as the A layer. A laminate was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-4)

A layer of 50 µm thick (A layer = 25 µm, B layer -A = 25 µm) in the same manner as in Example 3-1, except that the mixed mass ratio of Byron GM-443 and microscopic melamine was 25:75 as the A layer. A laminate was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-5)

After dry blending Byron GM-443 and fine-grained melamine at a mixing mass ratio of 60:40, kneading was carried out at 200 ° C using a 40 mm diameter coaxial twin screw extruder, and extruded from a T die and simultaneously cast B layer-A. By bonding from the roll side and the nip roll side, the laminated body of 70 micrometers in thickness (A layer = 20 micrometers, B layer -A = 25 micrometers) whose layer structure turns into B layer -A / A layer / B layer -A was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(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. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-7)

As a polyester-based resin (A), Toyo Spinning Co., Ltd. Byron GA-1300 (terephthalic acid: 32.8 mol%, isophthalic acid: 5.1 mol%, adipic acid: 12.1 mol%, 1,4-butanediol: 50 mol%, glass transition temperature A laminate having a thickness of 50 µm (A layer = 25 µm, B layer -A = 25 µm) was obtained in the same manner as in Example 3-2, except that = -6 ° C and ΔHm = 23.7 J / g were used. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-8)

Toyo Spinning Co., Ltd. Byron 30P (terephthalic acid: 27.0 mol%, isophthalic acid: 23.0 mol%, ethylene glycol: 50 mol%, glass transition temperature = -28 degreeC, (DELTA) Hm = 9.0 J / g) as polyester-type 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 as in Example 3-2 except for use. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-9)

After mixing Byron GM-443, Byron 30P and fine-grained melamine in mass ratio 20:40:40 as A-layer, it was 50 micrometers thick (A layer = 25 micrometers, B layer-A = in the same manner as Example 3-1. 25 micrometers) laminate was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-10)

Example 3-2, except for using GSPla AD92W (polybutylene succinate adipate copolymer, glass transition temperature = -40 ℃, ΔHm = 35 J / g) manufactured by Mitsubishi Chemical Corporation as the polyester resin (A) In the same manner, a laminate having a thickness of 50 μm (A layer = 25 μm, B layer-A = 25 μm) was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Examples 3-11)

Example 3- except that EcoFlex F (polybutylene adipate terephthalate copolymer, glass transition temperature = -30 degreeC, (DELTA) Hm = 21J / g) by BASF Corporation was used as polyester resin (A). In the same manner as in 2, a laminate having a thickness of 50 μm (A layer = 25 μm, B layer-A = 25 μm) was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-12)

Except for using GSPla AD92W (polybutylene succinate adipate copolymer, ΔHm = 35 J / g) manufactured by Mitsubishi Chemical Corporation as polyester-based resin (A), the thickness was 50 μm (A Layer = 25 μm, B layer-A = 25 μm). The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-13)

A laminate having a thickness of 50 μm was obtained in the same manner as in Example 3-1, except that the mixed mass ratio of GSPla AD92W and melamine was 40:60 as the A layer. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Example 3-14)

After dry blending GSPla AD92W and melamine at a mixing mass ratio of 60:40, they were kneaded at 200 ° C. using a 40 mm diameter coaxial twin screw extruder, and extruded from the T die, and layer (B) -A was cast on the cast roll side. By bonding from the nip roll side, the laminated body of 100 micrometers in thickness whose layer constitution becomes B layer -A / A layer / B layer -A was obtained. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(Examples 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. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(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. The result of having evaluated similarly to Example 3-1 about the obtained laminated body is shown in Table 3.

(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 performing the same evaluation as in Example 3-10 with respect to the obtained laminate.

(Comparative Example 3-1)

After blending Byron GM-443 and fine particle melamine in a mixing mass ratio of 60:40, the sheet | seat of 50 micrometers in thickness which B layer was not bonded was obtained by the method similar to Example 3-1. The result of having evaluated similarly to Example 3-1 about the obtained monolayer is shown in Table 4.

(Comparative Example 3-2)

The thickness of 50 µm (A layer = 25 µm, B layer -A = 25 µm) in the same manner as in Example 3-1, except that the mixed mass ratio of Byron GM-443 and microscopic melamine was 95: 5 as the A layer. A laminate was obtained. Table 4 shows the results of the same evaluations as in Example 3-1 regarding the obtained laminate.

(Comparative Example 3-3)

The mixed mass ratio of IUPEC PEC-350 and fine-grained melamine using IUPEC PEC-350 (polybutylene succinate carbonate copolymer, ΔHm = 55 J / g) manufactured by Mitsubishi Gas Chemical Co., Ltd. instead of the polyester resin (A). After dry blending to 60:40, the laminated body of 50 micrometers in thickness (A layer = 25 micrometers, B layer-A = 25 micrometer) was obtained by the same method as Example 3-1. Table 4 shows the results of the same evaluations as in Example 3-1 regarding the obtained laminate.

(Comparative Example 3-4)

By using Nissan Chemical Co., Ltd. MC-600 (melamine cyanurate) instead of fine-grained melamine, Byron GM-443 and MC-600 were blended at a mixed mass ratio of 60:40, and then the thickness was obtained in the same manner as in Example 3-1. A laminate of 50 μm (A layer = 25 μm, B layer-A = 25 μm) was obtained. Table 4 shows the results of the same evaluations as in Example 3-1 regarding the obtained laminate.

(Comparative Example 3-5)

By using Nippon Light Metal Co., Ltd. BF013ST (aluminum hydroxide) instead of fine-grained melamine, Byron GM-443 and BF013ST were blended at a mixing mass ratio of 60:40, and then 50 µm thick in the same manner as in Example 3-1 (A layer = 25 micrometers, B layer -A = 25 micrometers) was obtained. Table 4 shows the results of the same evaluations as in Example 3-1 regarding the obtained laminate.

(Comparative Example 3-6)

After blending GSPla AD92W and the fine-grained melamine in a mixed mass ratio of 60:40, a sheet having a thickness of 50 µm without bonding the B layer was obtained in the same manner as in Example 3-1. The result of having evaluated similarly to Example 3-1 about the obtained monolayer is shown in Table 4.

(Comparative Example 3-7)

A laminate having a thickness of 50 μm (A layer = 25 μm, B layer-A = 25 μm) in the same manner as in Example 3-1, except that the mixed mass ratio of GSPla AD92W and fine particle melamine was 95: 5 as the A layer. Got. Table 4 shows the results of the same evaluations as in Example 3-1 regarding the obtained laminate.

(Comparative Example 3-8)

Instead of melamine, GSPla AD92W and MC-600 were blended at a mixing mass ratio of 60:40 using MC-600 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd., and then laminated with a thickness of 50 µm in the same manner as in Example 3-1. Got a sieve. Table 4 shows the results of the same evaluations as in Example 3-1 regarding the obtained laminate.

(Comparative Example 3-9)

Instead of melamine, GSPla AD92W and BF013ST were blended with a mixed mass ratio of 60:40 using BF013ST (aluminum hydroxide) manufactured by Nippon Light Metal Co., Ltd., and a laminate having a thickness of 50 µm was obtained in the same manner as in Example 3-1. Table 4 shows the results of the same evaluations as in Example 3-1 regarding the obtained laminate.

From Table 3, the flame retardance of the third flame retardant laminates of Examples 3-1 to 17 passed UL94VTM, and the combustion time was low and good. Moreover, the 3rd flame-retardant laminated body of Examples 3-1-15 has sufficient peeling strength between A-layer and B-layer, is excellent in tensile strength, tensile elongation, heat resistance, and excellent in mechanical characteristics. Although the flame retardance was favorable for the 3rd flame-retardant laminated body of Examples 3-16 and 3-17, since B layer-C was used for B layer, it was not excellent in heat resistance.

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 less than 5 mass%, the flame retardancy is inferior to that of the third flame retardant laminate. Comparative Example 3-3 is inferior in flame retardancy compared with the third flame retardant laminate because the heat of fusion of crystals (ΔHm) of the polyester-based resin (A) is 50 J / g. 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. Since Comparative Example 3-6 does not have a B layer similarly to Comparative Example 3-1, the tensile strength, tensile elongation, and heat resistance are inferior to those of the third flame retardant laminate. In Comparative Example 3-7, the content of melamine was less than 5% by mass, so the flame retardancy was 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 mentioned above, since a 3rd flame-retardant laminated body uses specific polyester resin and uses specific amount of specific melamine, it has favorable flame retardance and mechanical characteristics. In particular, the third flame retardant laminate can be suitably used for applications such as flexible flat cables, electrical insulation materials, membrane switch circuit printing substrates, copier inner members, planar heating element substrates, and FPC reinforcing plates.

[Examples and Comparative Examples of Fourth Embodiment]

Next, the Example and comparative example which concern on 4th Embodiment is demonstrated.

The result shown in the Example was evaluated by the following method.

(1) flame retardant

It measured and evaluated similarly to the Example concerning 3rd Embodiment.

(2) adhesiveness with metal

As adhesive evaluation with a metal, the peeling strength between A layer and tin plating copper foil was measured by the method shown in FIG.

The peel strength was measured using a tensile tester (Intesco Co., Ltd. material testing machine 201X with a thermostat). The 180 degree peeling test was done at the atmospheric temperature of -20 degreeC, 23 degreeC, and 80 degreeC, and peeling rate of 10 mm / min using the thing of 10 mm width of the sample for evaluation. The peeling strength at all the temperatures was 5 N / 10 mm (that is, 5 N / cm) or more as the pass.

(3) heat resistance

The sample (flat cable) for evaluation of length 600mm x width 30mm (thickness differs with each test piece) is left to stand in the baking test apparatus (DKS-5S made from Taisei Scientific Co., Ltd.), and is 24 at 120 degreeC. Heated for hours.

The appearance of the sample after heating was visually observed, and there was no peeling of the copper foil, shrinkage of the flat cable, wrinkles, deformation, etc., and the occurrence of peeling of the copper foil, shrinkage of the flat cable, wrinkles, deformation, etc. Evaluated.

<Production of Layer B>

As a film which comprises B layer, the following two types of films ("B layer -A" "B layer -B") were manufactured and prepared.

`` B Layer-A '':

Using Novapex (polyethylene terephthalate, glass transition temperature = 79 ° C, ΔHm = 55 J / g) manufactured by Mitsubishi Chemical Corporation as a polyester resin, Novapex was first kneaded at 260 ° C with a 40 mmφ single screw extruder, It was extruded from the mold and then quenched with a casting roll of about 40 ° C. to prepare a amorphous sheet having a thickness of 225 μm. Subsequently, it was notified to Mitsubishi Hollow Co., Ltd. sequential biaxial tenter, it extended | stretched by 3 times of draw ratio in MD (length direction) at 95 degreeC, and extended | stretched by 3 times of draw ratio in TD (horizontal direction) at 110 degreeC. Furthermore, after that, it heat-processed at 160 degreeC for 15 second, and obtained the 25-micrometer-thick biaxially stretched film.

`` B Layer-B '':

Using coplyester6763 (polyethylene terephthalate glycol, glass transition temperature = 81 ° C, ΔHm = 0 J / g) manufactured by Eastman Chemical Co., Ltd. as a polyester resin, coplyester6763 was kneaded at 260 ° C with a 40 mm single screw extruder, and then detained. Was extruded from and then quenched with a casting roll of about 40 ° C. to prepare a 25 μm thick amorphous sheet.

(Example 4-1)

As a polyester-based resin (A), Toyo Spinning Co., Ltd. Byron GM-443 (terephthalic acid: 26.5 mol%, isophthalic acid: 19.8 mol%, adipic acid: 4.7 mol%, 1,4-butanediol: 50 mol%, glass transition temperature : 26 degreeC, the heat of fusion of crystals ((DELTA) Hm): 22.8 J / g), Melamine (average particle diameter: 5 micrometers) by Nissan Chemical Co., Ltd. was used as a flame retardant, The Japan epoxy resin company E4275 (bisphenol F / was used as a phenoxy resin. Bisphenol A = 75 mol% / 25 mol%) was used.

After dry blending these Byron GM-443, melamine, and E4275 in the ratio of the mixing mass ratio of 58/40/2, they were knead | mixed at 190 degreeC using the 40 mm diameter coaxial twin screw extruder, and the single screw extruder which attached the T type die | dye. The laminated film with a thickness of 65 micrometers whose layer constitution becomes A layer / B layer by melt | dissolving again into a sheet | seat, extruding in a sheet form from a mold | die, and extruding from a T die, and bonding "B layer-A" from the cast roll side. (A layer = 40 micrometers, B layer -A = 25 micrometers) was obtained.

The flame-retardant test was done about the obtained laminated | multilayer film, and the result was shown in Table 5.

Next, the tin-plated copper foil of thickness 150micrometer and width 10mm (both A layer inside) is arrange | positioned between two obtained laminated | multilayer films, and these are passed between metal rolls (heating) / rubber rolls (non-heating). It bonded together on the conditions of roll nip pressure 10 kg / cm (linear pressure), and the bonding speed of 0.5 m / min, and obtained the flat cable.

About the flat cable obtained by the said method, the result of having measured peeling strength and heat resistance of A layer and tin plating copper foil was shown in Table 5.

In addition, regarding a flame retardance, heat resistance, and the adhesiveness of A-layer and a tin-plated copper foil, when any one was unsuccessful, comprehensive evaluation was evaluated by "x", and when all the items passed the evaluation, comprehensive evaluation was evaluated by "(circle)". .

In addition, when the obtained flat cable was observed and peeling was seen between A-layer and B-layer, even if all said 3 items passed, it was set as "x" to evaluate.

(Example 4-2)

In the configuration of the layer A, the thickness was 65 µm (A layer = 25 µm, B layer-) in the same manner as in Example 4-1 except that the mixed mass ratio of Byron GM-443, melamine, and E4275 was 55: 40: 5. A = 40 micrometers) the laminated film was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 5.

(Example 4-3)

In the structure 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 mixed mass ratio of Byron GM-443, melamine, and E4275 was 50:40:10. A = 40 micrometers) the laminated film was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 5.

(Example 4-4)

As a polyester-based resin (A), Toyo Spinning Co., Ltd. Byron GA-1300 (terephthalic acid: 32.8 mol%, isophthalic acid: 5.1 mol%, adipic acid: 12.1 mol%, 1,4-butanediol: 50 mol%, glass transition temperature = -6 deg. C, ΔHm = 23.7 J / g), and 65 탆 thick in the same manner as in Example 4-1, except that the mixed mass ratio of Byron GA-1300, melamine, and E4275 was set to 50:40:10. A laminated film of A layer = 25 micrometers and B layer-A = 40 micrometers) was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 5.

(Example 4-5)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 5.

(Example 4-6)

Toyo Spinning Co., Ltd. Byron 30P as polyester resin (A) (terephthalic acid: 27.0 mol%, sebacic acid: 23.0 mol%, ethylene glycol: 50 mol%, glass transition temperature = -28 degreeC, (DELTA) Hm = 9.0 J / g) Using the same method as in Example 4-1, except that the mixed mass ratio of Byron 30P, melamine and E4275 was 50:40:10, a thickness of 65 µm (A layer = 25 µm, B layer -A = 40 µm) The laminated film of was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 5.

(Example 4-7)

In the configuration of the layer A, two kinds of the Byron GM-443 and 30P were used as the polyester resin (A), and the mixed mass ratio of Byron GM-443, Byron 30P, melamine and E4275 was set to 35:20:40: 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 value was 5.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 5.

(Example 4-8)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 5.

(Example 4-9)

In the structure 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 mixed mass ratio of Byron GM-443, melamine, and E4275 was 35: 60: 5. A = 40 micrometers) the laminated film was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 6.

(Example 4-10)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to 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 mixed mass ratio of Byron GM-443, melamine, and E4275 was 28: 70: 2. A = 40 micrometers) the laminated film was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 6.

(Example 4-12)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to 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 mixed mass ratio of Byron GM-443, melamine, and E4275 was 35:40:25. A = 40 micrometers) the laminated film was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 6.

(Example 4-14)

65 µm thick (A layer = 25 µm, B layer -A = 40 µm in the same manner as in Example 4-1, except that the mixed mass ratio of Byron GM-443, melamine, and E4275 was set to 30:40:30 as the A layer. ) Laminated film.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 6.

(Example 4-15)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 6.

(Example 4-16)

GSPla AZ91T (polybutylene succinate, glass transition temperature: -30 degreeC, (DELTA) Hm: 54.0 J / g) by Mitsubishi Chemical Corporation was used as polyester-type resin (A), and GSPla AZ91T and melamine in the structure of A layer. 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 mixed mass ratio of E4275 was 55: 40: 5.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 6.

(Comparative Example 4-1)

In the configuration of the A layer, without blending a phenoxy resin, Byron GM-443 and melamine were blended in a mixing mass ratio of 60:40, and then 65 µm thick (A layer = 25 µm) in the same manner as in Example 4-1. , B layer-A = 40 μm), to obtain a laminated film.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

(Comparative Example 4-2)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

(Comparative Example 4-3)

In the configuration of the A layer, instead of melamine, MC-600 (melamine cyanurate) manufactured by Nissan Chemical Industry Co., Ltd. was used, and Byron GM-443, MC-600, and E4275 were blended in a mixed mass ratio of 55: 40: 5, In the same manner as in Example 4-1, a laminated film having a thickness of 65 μm (A layer = 25 μm, B layer-A = 40 μm) was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

(Comparative Example 4-4)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

(Comparative Example 4-5)

Except for using "B layer-B" instead of "B layer-A" as the film constituting the B layer, the thickness was 65 µm in the same manner as in Example 4-2 (A layer = 40 µm, B layer -C = 25 The laminated film of (micrometer) was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

(Comparative Example 4-6)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to 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 mixed mass ratio of Byron GM-443, melamine, and E4275 was 25:40:35. A = 40 micrometers) the laminated film was obtained.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

(Comparative Example 4-8)

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

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

(Comparative Example 4-9)

65 µm thick (A layer = 25 µm, B layer -A = 40 µm in the same manner as in Example 4-1, except that the mixed mass ratio of Byron GM-443, melamine, and E4275 was set to 13: 85: 2 as the A layer. ) Laminated film.

About the obtained laminated | multilayer film, the same evaluation as Example 4-1 was performed, and the flat cable was produced and evaluated similarly to Example 4-1. The results are shown in Table 7.

From the evaluation results of Examples 4-1 to 16, in the A layer as the adhesive layer, VTM-0 in the UL94 vertical combustion test by blending phenoxy resin with melamine in a polyester resin having a specific glass transition temperature. In addition to the high flame retardancy which is passed, it has been found that excellent heat resistance and further excellent adhesion with a metal conductor can be obtained.

For example, when comparing Example 4-1 and Comparative Example 4-1 which did not mix | blend a phenoxy resin, it became clear that by mix | blending a phenoxy resin, adhesiveness with a metal conductor becomes remarkably high and heat resistance also becomes high. It became.

Moreover, when comparing the comparative example 4-3 and the Example which used melamine cyanurate other than melamine, it turned out that flame retardance can be remarkably improved by using melamine. Since melamine generates a non-combustible gas at the time of combustion, not only can the flame-retardant adhesive layer be flame-retarded, but also the outer layer (B layer) which does not contain a flame retardant can be flame retarded, so that the flame retardancy of the laminated film is particularly increased. Can be.

In addition, although the adhesiveness with copper plating tin was examined in the said test, since adhesion of a phenoxy resin and a metal can be considered to be due to the hydrogen bond of the water and phenoxy resin which exist in a metal surface, it is other than copper plating tin. It is considered that the same adhesiveness can be obtained also for a metal (for example, silver, gold, platinum, iron, stainless steel, steel, or an alloy thereof).

Compared with Example 4-1, Examples 4-4-7 use polyester-based resin (A) from which glass transition temperature and (DELTA) Hm differ. Considering these results and previous experiences, the polyester resin (A) has a low Tg, high peel strength at low temperature (for example, 0 ° C. or lower), and high ΔHm. Since it is high, it turned out that heat resistance tends to become high.

From this point of view, the glass transition temperature of the polyester-based resin (A) is preferably -80 ° C or higher, particularly -70 ° C or higher, particularly -60 ° C or higher, more preferably 30 ° C or lower, particularly 20 It can be considered that it is 10 degrees C or less, especially below 10 degreeC.

Moreover, it is preferable that the crystal melting heat amount ((DELTA) Hm) of polyester-type resin (A) is 5-30 J / g, Moreover, it is especially preferable that it is 8 J / g or more, especially 10 J / g or more, and an upper limit Silver is especially 25 J / g or less, and it can be considered that it is more preferable especially 20 J / g or less.

On the other hand, regarding polyester resin (B), when it considers considering the evaluation result of the said Example and a comparative example, especially the evaluation result of Comparative Example 4-5 and the past experience, it is the case of polyester resin (B). It is preferable that glass transition temperature is 50-120 degreeC, and as a lower limit, it is especially preferable that it is 55 degreeC or more, especially 60 degreeC or more, and it can be considered that an upper limit is especially 110 degreeC or less, especially 100 degreeC or less. have.

Moreover, it is preferable that the crystal melting heat amount ((DELTA) Hm) of polyester-type resin (B) is 40-100 J / g, As a lower limit, it is especially preferable that it is 45 J / g or more, especially 50 J / g or more, It is considered that the upper limit is particularly preferably 90 J / g or less, especially 80 J / g or less.

From the result of the said Example and a comparative example, and previous experience, it is preferable that the compounding ratio of melamine which occupies in the resin composition (a) which comprises A-layer is 20-80 mass%, and the minimum value is 30 mass% or more especially. Especially, it is more preferable that it is 40 mass% or more, and it can be considered that an upper limit is 70 mass% or less especially, and it is more preferable that it is 60 mass% or less especially.

Moreover, it is preferable that the ratio of the phenoxy resin in the resin composition (a) which comprises A-layer is 1-30 mass%, It is more preferable that a lower limit is 5 mass% or more, and it is more preferable that the upper limit is 20 mass% or less. It can be considered preferable.

Moreover, when comparing with Example 4-15 and the other Example and considering the experience so far, the reason is not clear, but it turned out that bisphenol F is more flame retardant than bisphenol A among bisphenol.

[Examples and Comparative Examples of Fifth Embodiment]

Next, the Example and comparative example which concern on 5th Embodiment is demonstrated.

(1) flame retardant

It measured and evaluated similarly to the Example concerning 3rd Embodiment.

(2) tensile strength, tensile elongation

It measured and evaluated similarly to the Example concerning 3rd Embodiment.

(3) heat resistance (softening temperature)

The softening temperature by TMA was measured based on JISK7196 using the sample for evaluation of length 5mm x width 5mm (thickness differs with each test piece). The TMA curve was measured at an ambient temperature of 23 ° C., a relative humidity of 50%, a pressure of 0.5 N against the indenter, and a rate of increase of 5 ° C./min. The intersection point with the extension to the low temperature side of the tangent of the part where the penetration speed is maximum is set as the penetration penetration temperature, and the softening temperature was calculated from this value. The softening temperature made 140 degreeC or more pass.

<Production of Layer B>

`` B Layer-1 ''

Using Novafex (polyethylene terephthalate, glass transition temperature = 79 ° C, ΔHm = 55 J / g) manufactured by Mitsubishi Chemical Corporation as a polyester resin, Novafex was first kneaded at 260 ° C with a 40 mm diameter single screw extruder, It was extruded from the mold and then quenched with a casting roll of about 40 ° C. to prepare a amorphous sheet having a thickness of 225 μm. Subsequently, it was notified to Mitsubishi Hollow Co., Ltd. sequential biaxial tenter, it extended | stretched by 3 times of draw ratio in MD (length direction) at 95 degreeC, and extended | stretched by 3 times of draw ratio in TD (horizontal direction) at 110 degreeC. Furthermore, after that, it heat-processed at 160 degreeC for 15 second, and obtained the 25-micrometer-thick biaxially stretched film.

`` B Layer-2 ''

After producing the amorphous sheet of 108 micrometers in thickness by the method and conditions similar to the said B layer-1, it extended | stretched by the same method and conditions as the said B layer-1, and obtained the biaxially stretched film of 12 micrometers in thickness.

`` B Layer-3 ''

A biaxially oriented film having a thickness of 25 µm in the same manner as in the "B layer-1", except that NW4032D (polylactic acid, glass transition temperature = 55 ° C, ΔHm = 42 J / g) manufactured by Nature Works was used as the polyester resin. Got.

(Example 5-1)

GSPla AZ91T (polybutylene succinate, glass transition temperature = -30 ° C, ΔHm = 54.0 J / g) manufactured by Mitsubishi Chemical Corporation, finely divided melamine (melamine) manufactured by Nissan Chemical Industries, Ltd. and TMAIC (trimethalyl) manufactured by Nippon Chemical Co., Ltd. Isocyanate), GSPla AZ91T, finely divided melamine and TMAIC were dry blended at a mixing mass ratio of 69: 30: 1, and kneaded at 190 ° C using a 40 mm diameter coaxial twin screw extruder, and 55 ° C. The sheet (A layer) of 50 micrometers in thickness was obtained with the casting roll of. Subsequently, by laminating B layer-1 as both outer layers of the A layer from the cast roll side and the nip roll side, a laminate having a thickness of 100 μm in which the layer configuration became B-1 / A / B-1 was obtained. Subsequently, radiation (γ-ray) was irradiated to the laminate with an irradiation dose of 50 kGy. Table 8 shows the results of evaluation of the gel fraction, flame retardancy, tensile strength, elongation and heat resistance of the obtained laminate.

(Example 5-2)

The laminated body was produced and evaluated in the same manner as in Example 5-1 except that the mixed mass ratio of GSPla AZ91T, finely divided melamine and TMAIC was 59: 40: 1. The results are shown in Table 8.

(Example 5-3)

The laminated body was produced and evaluated in the same manner as in Example 5-1 except that the mixed mass ratio of GSPla AZ91T, finely divided melamine, and TMAIC was 49: 50: 1. The results are shown in Table 8.

(Example 5-4)

The laminated body was produced and evaluated in the same manner as in Example 5-1 except that the mixed mass ratio of GSPla AZ91T, finely divided melamine, and TMAIC was 59.5: 40: 0.5. The results are shown in Table 8.

(Example 5-5)

The laminated body was produced and evaluated in the same manner as in Example 5-1 except that the mixed mass ratio of GSPla AZ91T, finely divided melamine and TMAIC was changed to 57: 40: 3. The results are shown in Table 8.

(Example 5-6)

In Example 5-2, the laminate was manufactured and evaluated in the same manner except that the thickness of the A layer was 20 μm. The results are shown in Table 8.

(Example 5-7)

In Example 5-3, the laminate was manufactured and evaluated in the same manner except that the thickness of the A layer was 70 μm. The results are shown in Table 8.

(Example 5-8)

In Example 5-2, the thickness of A layer was 30 micrometers, and the laminated body was manufactured and evaluated by the same method except having used B-2 as B layer. The results are shown in Table 8.

(Example 5-9)

The mixture mass ratio of GSPla AZ91T, finely divided melamine and TMAIC was 39: 60: 1, the thickness of the A layer was 35 µm, and B layer-2 was used as the B layer. Manufacture and evaluation were performed. The results are shown in Table 8.

(Example 5-10)

As the polyester resin (A), GSPla AD92W (polybutylene succinate adipate copolymer, glass transition temperature = -40 ° C, ΔHm = 35 J / g) manufactured by Mitsubishi Chemical Corporation was used, and GSPla AD92W, finely divided melamine and After TMAIC was dry blended with a mixing mass ratio of 59: 40: 1, the laminated body was manufactured and evaluated by the method similar to Example 5-1. The results are shown in Table 8.

(Example 5-11)

The laminated body was produced and evaluated in the same manner as in Example 5-1, except that the mixed mass ratio of GSPla AD92W, finely divided 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 Chemical Co., Ltd. was used as a crosslinking agent, and the mixed mass ratio of GSPla AZ91T, finely divided melamine and DA-MGIC was 59: 40: 1. The laminated body was manufactured and evaluated by the same method. The results are shown in Table 8.

(Comparative Example 5-1)

The laminated body was produced and evaluated in the same manner as in Example 5-1 except that the mixed mass ratio of GSPla AZ91T, finely divided melamine and TMAIC was 84: 15: 1. The results are shown in Table 8.

(Comparative Example 5-2)

The laminated body was produced and evaluated in the same manner as in Example 5-1 except that the mixed mass ratio of GSPla AZ91T, finely divided 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)

In Example 5-2, the result of having manufactured and evaluated the laminated body without mix | blending a crosslinking agent is shown in Table 8.

(Comparative Example 5-4)

The same A layer as in Example 5-2 was produced, and the monolayer which did not bond B layer was manufactured and evaluated. The results are shown in Table 8.

(Comparative Example 5-5)

In Example 5-3, the laminate was manufactured and evaluated in the same manner except that the thickness of the A layer was 10 μm. The results are shown in Table 8.

(Comparative Example 5-6)

Instead of melamine, MC-860 (melamine cyanurate) manufactured by Nissan Chemical Industries, Ltd. was used, and the mixed mass ratio of GSPla AZ91T, MC-860, and TMAIC was 59: 40: 1, in the same manner as in Example 5-1. The laminated body was manufactured and evaluated. The results are shown in Table 8.

(Comparative Example 5-7)

Production of a laminate in the same manner as in Example 5-1, except that Showa Denko H42S (aluminum hydroxide) was used instead of melamine, and the mixed mass ratio of GSPla AZ91T, H42S and TMAIC was 59: 40: 1. Evaluation was performed. The results are shown in Table 8.

(Comparative Example 5-8)

Toyo Spinning Co., Ltd. Byron (registered trademark) GA1310 (polyester-based copolymer (35 mol% of terephthalic acid, 15 mol% of isophthalic acid, 50 mol% of 1,4-butanediol), glass transition temperature = 27 ° C, ΔHm = 26.1 J / g) was used, and the laminated body was produced and evaluated in the same manner as in Example 5-3, except that the mixed mass ratio of GA1310, finely divided melamine and TMAIC was 49: 50: 1. The results are shown in Table 8.

(Comparative Example 5-9)

In Example 5-3, the laminate was manufactured and evaluated in the same manner except that B layer-3 was used as the B layer. The results are shown in Table 8.

From Table 8, since the flame retardance of the laminated body of Examples 5-1-12 passed UL94VTM, the combustion time was small and favorable, heat resistance, etc. were favorable, and mechanical strength was enough, the comprehensive evaluation became (circle).

On the other hand, the comparative example 5-1 was inferior in flame retardance because the mass% with respect to the whole laminated body of melamine was not in the predetermined range. Since the comparative example 5-2 had the mass% with respect to the whole laminated body of melamine not in a predetermined range, tensile strength, tensile elongation, and softening temperature were inferior. In Comparative Example 5-3, the gel fraction was not within a predetermined range without adding a crosslinking agent, and the softening temperature was inferior. Since the comparative example 5-4 did not arrange | position B layer, tensile strength, tensile elongation, and softening temperature were inferior. Since the thickness of A-layer was thin in Comparative Example 5-5, the mass% with respect to the whole laminated body of melamine was low, and the flame retardance was inferior. Since the comparative example 5-6 added not melamine but melamine cyanurate, flame retardance was inferior. Since Comparative Example 5-7 added aluminum hydroxide instead of melamine, the flame retardance was inferior. In Comparative Example 5-8, since the polyester resin (A) did not have a predetermined glass transition temperature, the tensile elongation was inferior. In Comparative Example 5-9, since the polyester-based resin (B) did not have a predetermined glass transition temperature, the softening temperature was low and inferior in heat resistance.

As mentioned above, since the laminated body which concerns on 5th Embodiment uses specific polyester resin and uses specific amount of specific melamine, it has favorable flame retardance and heat resistance. Moreover, the wiring cable, flat cable, electrical insulation material, membrane switch circuit printing base material, copier inner member, planar heating element base material, FPC reinforcement board, etc. which were manufactured from the laminated body which concerns on 5th Embodiment have favorable flame retardance, heat resistance, and bendability. Do.

[Examples and Comparative Examples of Sixth Embodiment]

Next, the Example and comparative example which concerns on 6th Embodiment is demonstrated.

(1) Flame retardant (UL94VTM) (laminate)

The test number of 5 circuits was burned based on the procedure of the safety standard UL94 vertical combustion test of Underwriters Laboratories, using an evaluation sample (laminate) of 200 mm in length x 50 mm in width (thickness differs for each test piece). The test was conducted.

Based on the criterion of UL94 vertical combustion test UL94VTM, what satisfied the VTM-0 standard was made into (circle), and what did not satisfy | filled was made into x.

(2) Flame Retardant (UL1581VW-1) (Flat Cable)

Evaluation sample (flat cable) of 600 mm in length x 19 mm in width (thickness varies according to each test piece) is ignited for 15 seconds using a Tyrryl burner based on the combustion test method of UL1581VW-1 standard. The second pause was repeated five times, and determination was made based on the burning time of the test piece, the damage ratio of the indicator, and the presence or absence of ignition of cotton wool due to the drip. The UL1581VW-1 pass was made that the combustion time was 60 seconds or less, the damage rate of an indicator was 25% or less, and there was no ignition of the cotton wool by a drip. In Table 9, the thing with a pass and the thing with reject were described with x.

(3) heat resistance

The sample (flat cable) for evaluation of length 600mm x width 30mm (thickness differs with each test piece) is left to stand in the baking test apparatus (DKS-5S made from Taisei Scientific Co., Ltd.), and is 24 at 120 degreeC. Heated for hours.

The appearance of the sample after heating was visually observed, and there was no peeling of the copper foil, shrinkage of the flat cable, wrinkles, deformation, etc., and the occurrence of peeling of the copper foil, shrinkage of the flat cable, wrinkles, deformation, etc. Evaluated.

(4) bendability

A sample (flat cable) for evaluation of 600 mm in length x 30 mm in width (thickness varies depending on each test piece) was visually observed for bending at 180 degrees, and peeling and cracking of the copper foil and the adhesive occurred. What was not evaluated was evaluated as "(circle)" and what was generated by "x".

<Production of Layer B>

As a film which comprises B layer, the following two types of films ("B layer -A" "B layer -B") were manufactured and prepared.

`` B Layer-A '':

Using Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation (polyethylene terephthalate, glass transition temperature = 79 ° C, ΔHm = 55 J / g) as the polyester-based resin, Novapex was first subjected to a 40 mm diameter single screw extruder at 260 ° C. After kneading, it was extruded from a mold and then quenched with a casting roll of about 40 ° C. to prepare a amorphous sheet having a thickness of 225 μm. Subsequently, it was notified to Mitsubishi Hollow Co., Ltd. sequential biaxial tenter, it extended | stretched by 3 times of draw ratio in MD (length direction) at 95 degreeC, and extended | stretched by 3 times of draw ratio in TD (horizontal direction) at 110 degreeC. Furthermore, after that, it heat-processed at 160 degreeC for 15 second, and obtained the 25-micrometer-thick biaxially stretched film.

`` B Layer-B '':

Coplyester6763 (polyethylene terephthalate glycol, glass transition temperature = 81 ° C, ΔHm = 0 J / g) manufactured by Eastman Chemical Co., Ltd. was used as a polyester resin, and coplyester6763 was kneaded at 260 ° C with a 40 mm diameter single screw extruder, and then detained. Was extruded from and then quenched with a casting roll of about 40 ° C. to prepare a 25 μm thick amorphous sheet.

(Example 6-1)

As a polyester-based resin (A), Byron Spinning Co., Ltd. Byron (registered trademark) GM-480 (terephthalic acid: 45 mol%, sebacic acid: 5 mol%, 1,4-butanediol: 50 mol%, glass transition temperature: -2 ℃, crystal melting heat (ΔHm): 24.6 J / g), Nissan Chemical Co., Ltd. fine powder melamine (average particle size 5 ㎛) was used as a flame retardant, Tomoe Kogyo PKHB (phenoxy resin) was used as a carbonization accelerator. .

These Byron GM-480, melamine and PKHB were dry blended at a mixing mass ratio of 55: 40: 5, and then kneaded at 190 ° C using a 40 mm diameter coaxial twin screw extruder, and a single-axis attached with a T-type die. It melt | dissolves again with an extruder, and extrudes into a sheet form from a mold | die, extrudes from a T die, and laminates a thickness of 65 micrometers whose layer constitution becomes A layer / B layer by bonding "B layer-A" from the cast roll side. A sieve (A layer = 40 µm, B layer-A = 25 µm) was obtained.

Next, the tin-plated copper foil of thickness 150micrometer and width 10mm (both A layer inside) is arrange | positioned between two obtained laminated bodies, and these are passed between metal rolls (heating) / rubber rolls (non-heating). It bonded together on the conditions of roll nip pressure 10 kg / cm (linear pressure), and the bonding speed of 0.5 m / min, and obtained the flat cable.

Table 9 shows the results of evaluating the flame retardance (UL94VTM) for the laminate obtained by the above method, the flame retardance (UL1581VW-1), the heat resistance, and the bendability for the flat cable.

In addition, in the case of failure at least for flame retardancy, heat resistance, and bendability, comprehensive evaluation was evaluated by "x", and when all the items passed the evaluation, comprehensive evaluation was evaluated by "(circle)".

In addition, when the obtained flat cable was observed and peeling was seen between A-layer and B-layer, even if all said 3 items passed, it was set as "x" to evaluate.

(Example 6-2)

In the configuration of the layer A, the thickness was 65 µm (A layer = 25 µm, B layer-) in the same manner as in Example 6-1, except that the mixed mass ratio of Byron GM-480, melamine, and PKHB was 50:40:10. A = 40 micrometers) was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-3)

Nissan Chemical Industry Co., Ltd. MC-600 (melamine cyanurate) was used as the carbonization accelerator, and the mixed mass ratio of Byron GM-480, Melamine, and MC-600 was 40: 40: 20 in the structure of the A layer. In the same manner as in Example 6-1, a laminate having a thickness of 65 μm (A layer = 25 μm, B layer-A = 40 μm) was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-4)

Using pentaerythritol manufactured by Junsei Chemical Co., Ltd. as a carbonization accelerator, the same composition as in Example 6-1 except that the mixed mass ratio of Byron GM-480, melamine, and pentaerythritol was 40:40:20 in the structure of the A layer. The laminated body of thickness 65micrometer (A layer = 25micrometer, B layer-A = 40micrometer) was obtained by the method. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-5)

Aluminum hydroxide manufactured by Nakarayesque Co., Ltd. was used as the carbonization accelerator, and the composition mass of A layer was the same as that in Example 6-1 except that the mixed mass ratio of Byron GM-480, melamine and aluminum hydroxide was set to 50:40:10. The laminated body of thickness 65micrometer (A layer = 25micrometer, B layer-A = 40micrometer) was obtained by the method. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-6)

In the configuration of the A layer, the thickness was 65 µm (A layer = 25 µm, B layer -A = 40 µm) in the same manner except that the mixed mass ratio of Byron GM-480, melamine and MC-600 was set to 50:30:20. ) Was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-7)

In the configuration of the A layer, the thickness was 65 µm (A layer = 25 µm, B layer -A = 40 µm) by the same method except that the mixed mass ratio of Byron GM-480, melamine and PKHB was 35: 60: 5. A laminate was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-8)

In the structure of the A layer, the thickness was 65 µm (A layer = 25 µm, B layer-by the same method except that the mixed mass ratio of Byron GM-480, melamine, PKHB, and MC-600 was 35: 40: 5: 20). A = 40 micrometers) was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body 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-by the same method except that the mixed mass ratio of Byron GM-480, melamine, PKHB, and pentaerythritol was set to 45: 40: 5: 10). A = 40 micrometers) was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-10)

As polyester-based resin (A), Toyo Spinning Co., Ltd. Byron (registered trademark) GM-443 (terephthalic acid: 27 mol%, isophthalic acid: 19 mol%, adipic acid: 4 mol%, 1,4-butanediol: 50 mol% , Glass transition temperature: 26 ° C., heat of fusion of crystals (ΔHm): 22.8 J / g), and the mixed mass ratio of Byron GM-443, melamine and MC-600 was 40:40:20 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 for setting it as the above. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Example 6-11)

Toyo Spinning Co., Ltd. Byron (registered trademark) 30P (terephthalic acid: 27 mol%, sebacic acid: 23 mol%, ethylene glycol: 50 mol%, glass transition temperature: -28 deg. (ΔHm): 2.0 J / g), and in the configuration of the A layer, the same method as in Example 6-1 except that the mixed mass ratio of Byron 30P, 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. Next, a flat cable was manufactured in the same manner as in Example 6-1.

Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Comparative Example 6-1)

In the configuration of the A layer, the thickness was 65 µm (A layer = 25 µm, B layer -A = 40 µm) in the same manner except that the mixed mass ratio of Byron GM-480, melamine and MC-600 was 70:10:20. ) Was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1.

Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Comparative Example 6-2)

In the configuration of the A layer, the thickness was 65 µm (A layer = 25 µm, B layer -A = 40 µm) in the same manner except that the mixed mass ratio of Byron GM-480, melamine and PKHB was 5: 90: 5. A laminate was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Comparative Example 6-3)

In the configuration of the layer A, 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 mixed mass ratio of 60:40. . Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body 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) by the same method except that the mixed mass ratio of Byron GM-480, melamine and MC-600 (melamine cyanurate) was 40:10:50. Layer-A = 40 mu m) to obtain a laminate. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Comparative Example 6-5)

Except for using "B layer-B" instead of "B layer-A" as the film constituting the B layer, the thickness was 65 µm in the same manner as in Example 6-3 (A layer = 40 µm, B layer -C = 25 A laminate of μm) was obtained. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

(Comparative Example 6-6)

NW4032D (polylactic acid, glass transition temperature: 55 degreeC, crystal melting heat ((DELTA) Hm): 42.5 J / g) manufactured by Nature Works) was used as polyester resin (A), and NW4032D and melamine in the structure of A layer. And a laminated body having a thickness of 65 µm (A layer = 25 µm, B layer -A = 40 µm) in the same manner as in Example 6-1 except that the mixed mass ratio of MC-600 was 40:40:20. Next, a flat cable was manufactured in the same manner as in Example 6-1. Evaluation similar to Example 6-1 was performed using the obtained laminated body and flat cable. The results are shown in Table 9.

From Table 9, the flame retardance of the laminated bodies of Examples 6-1-11 passed UL94VTM, and the combustion time was few and favorable. In addition, the flat cables produced by the laminates of Examples 6-1 to 11 had a small combustion time, passed UL1581VW-1, had good heat resistance, and had good bendability. It became.

On the other hand, in Comparative Example 6-1, since the ratio of melamine added to the laminate was small, the flame retardancy of the laminate and the flat cable was inferior. Since the comparative example 6-2 had many ratios of the melamine added to a laminated body, the bendability of the flat cable was inferior. In Comparative Example 6-3, since the carbonization accelerator was not added to the laminate, the flame retardancy in the laminate was good, but the flame retardancy of the flat cable was inferior. Since the comparative example 6-4 had many ratios of the melamine cyanurate added to a laminated body, and the ratio of melamine was small, the flame retardance of the laminated body was favorable but the flame retardance of the flat cable was inferior. Since Comparative Example 6-5 used resin whose (DELTA) Hm was not the range of this invention for B layer, the flame retardance of the laminated body was favorable but the heat resistance of the flat cable was inferior. In Comparative Example 6-6, the polyester resin (A) did not fall within the scope of the present invention, and thus, the flame retardance, heat resistance, and bendability were inferior.

As mentioned above, since the laminated body which concerns on 6th Embodiment uses specific polyester resin and uses specific amount of specific melamine, it has favorable flame retardance and is suitable for manufacturing a wiring cable. Moreover, the wiring cable (flat cable, electrical insulation material, membrane switch circuit printing base material, copier inner member, planar heating element base material, FPC reinforcement board, etc.) manufactured with the laminated body which concerns on 6th Embodiment is flame-retardant, heat resistance, and bendability Good.

As mentioned above, although this invention was demonstrated with reference to embodiment which is considered most practical and preferable at this time, this invention is not limited to embodiment disclosed in this specification, The summary of invention read from the Claim and the whole specification. Or it can change suitably in the range which is not contrary to an idea, It is to be understood that the antistatic resin molding which accompanied such a change, and the manufacturing method of this molding are also included in the technical scope of this invention.

Claims (25)

As a flame-retardant polyester-type resin composition containing the mixture of polyester resin and melamine whose glass transition temperature (Tg) is 40 degrees C or less, and crystal melting temperature (Tm) is 140 to 190 degreeC,
The proportion of melamine in the flame retardant polyester resin composition is 10 to 80% by mass, the flame retardant polyester resin composition. The method of claim 1,
It is polyester resin whose glass transition temperature (Tg) is -20 degreeC-40 degreeC, and crystal melting temperature (Tm) is 140 degreeC-190 degreeC, and glass transition temperature (Tg) is -100 degreeC or more and less than -20 degreeC, As a flame-retardant polyester-type resin composition containing the mixture of polyester-type resin and melamine whose crystal melting temperature (Tm) is 100 degreeC or more and less than 140 degreeC,
The proportion of melamine in the flame retardant polyester resin composition is 20 to 60 mass%, and the mass ratio of the former polyester resin and the latter polyester resin is 90:10 to 30:70. Ester resin composition. The method of claim 1,
The polyester resin contains 50 to 90 mol% of terephthalic acid as the polyhydric carboxylic acid component, and 70 to 100 mol% in total of 1,4-butanediol, ethylene glycol and diethylene glycol as the polyhydric alcohol component. A flame retardant polyester resin composition characterized by the above. The method of claim 1,
The flame retardant polyester resin composition comprises a phenoxy resin. The method of claim 4, wherein
A flame retardant polyester resin composition containing a mixture of a polyester resin, melamine and a phenoxy resin,
The polyester resin contains 50 to 90 mol% of terephthalic acid as the polyhydric carboxylic acid component and 70 to 100 mol% in total of 1,4-butanediol, ethylene glycol and diethylene glycol as the polyhydric alcohol component. 1 feature,
The flame-retardant polyester-based resin composition characterized by the 2nd characteristic that the ratio of the melamine which occupies for a flame-retardant polyester-based resin composition is 10-60 mass%, and the ratio of a phenoxy resin is 1-25 mass%. The method of claim 1,
The flame retardant polyester resin composition contains a carbonization accelerator. The method according to claim 6,
The said carbonization promoter is a compound which has a hydroxyl group, The flame-retardant polyester resin composition characterized by the above-mentioned. The method according to claim 6,
Flame retardant polyester resin composition, characterized in that the carbonization accelerator is melamine cyanurate. The method of claim 1,
The flame retardant polyester resin composition comprises a crosslinking agent. The method of claim 9,
Flame-retardant polyester resin composition, characterized in that the crosslinking agent is trimethallyl isocyanate. The flame-retardant resin body which consists of a flame-retardant polyester-type resin composition of Claim 1. The flame-retardant resin body which consists of a flame-retardant polyester-type resin composition of Claim 2. The flame-retardant resin body which consists of a flame-retardant polyester-type resin composition of Claim 4. The flame-retardant laminated body which has another resin layer on at least 1 surface of the resin layer which consists of a flame-retardant polyester-type resin composition of Claim 1. The flame-retardant laminated body which has another resin layer on at least 1 surface of the resin layer which consists of a flame-retardant polyester-type resin composition of Claim 2. The flame-retardant laminated body which has another resin layer on at least 1 surface of the resin layer which consists of a flame-retardant polyester-type resin composition of Claim 4. 15. The method of claim 14,
The said other resin layer is a layer which consists of a resin composition containing the polyester-based resin whose glass transition temperature is 50 degreeC or more and crystal heat quantity ((DELTA) Hm) is 40 J / g or more, The flame-retardant resin laminated body characterized by the above-mentioned. 15. The method of claim 14,
It has A layer which consists of a resin composition (a) which has a mixture of polyester resin, melamine, and phenoxy resin whose glass transition temperature is -80-30 degreeC as a main component, and a glass transition temperature is 50- on this A layer. As a resin laminated body which has a B layer which consists of a resin composition (b) which is 120 degreeC and has a polyester resin whose crystal melting heat ((DELTA) Hm) is 40-100 J / g as a main component,
The proportion of melamine in the resin composition (a) constituting the A layer is 20 to 80 mass%, and the proportion of the phenoxy resin in the resin composition (a) is 1 to 30 mass%. sieve. 15. The method of claim 14,
It has A layer which consists of resin composition (a) which has a mixture of polyester resin, melamine, and a carbonization accelerator whose glass transition temperature is 30 degrees C or less as a main component,
The lamination which has B layer which consists of a resin composition (b) which has a glass transition temperature of 50-120 degreeC on the said A layer, and polyester-based resin whose crystal melting heat amount ((DELTA) Hm) is 40-100 J / g as a main component. As a sieve,
The proportion of melamine in the resin composition (a) constituting the A layer is 20 to 80 mass%, and the proportion of the carbonization accelerator in the resin composition (a) is 1 to 30 mass%. . The method of claim 18,
A flame-retardant resin laminate characterized by being for metal bonding. The method of claim 19,
A flame-retardant resin laminate characterized by being for metal bonding. 15. The method of claim 14,
As a laminated body which has a B layer whose main component is a polyester resin whose glass transition temperature is 60 degreeC or more on at least one side of A-layer which has a mixture of polyester resin, melamine, and a crosslinking agent whose glass transition temperature is 20 degrees C or less as a main component. ,
The gel fraction of the said laminated body is 15 mass% or more and 55 mass% or less, and the ratio of the melamine which occupies for a laminated body is 10 mass% or more and 40 mass% or less, The flame-retardant resin laminated body characterized by the above-mentioned. Wiring cable using the flame-retardant polyester-based resin composition of Claim 1. The wiring cable using the flame-retardant resin body of Claim 11. The wiring cable using the flame-retardant resin laminated body of Claim 14.

Images