JP2010132833A - Flame-retardant polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new flame-retardant polyester resin composition with flame retardancy and stress relaxation properties. <P>SOLUTION: This flame-retardant polyester resin composition includes a mixture of a polyester resin (A), melamine (B), and a phenoxy resin (C), wherein firstly the polyester resin (A) contains 50-90 mol% of terephthalic acid as a polycarboxylic acid component, and 70-100 mol% of the total of 1,4-butane diol, ethylene glycol, and diethylene glycol as a polyhydric alcohol component; and secondly, on the basis of the resin composition, a content of the melamine (B) is 10-60 mass%, and a content of the phenoxy resin (C) is 1-25 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame retardant polyester resin composition having flame retardancy and stress relaxation properties.

  Polyester resins with excellent insulation and flexibility are attracting attention as alternative materials for vinyl chloride resins. However, polyester resins are generally easy to burn, so it is difficult to make these resins flame-retardant. It is necessary to add flame retardant to make it flame retardant.

As flame retardants for polyester resins, halogen flame retardants such as decabromodiphenyl ether and hexabromodiphenyl have been used. Halogen flame retardants generate harmful gases such as dioxins during combustion. In some cases, it was also a problem in terms of safety during waste incineration and thermal recycling.
Phosphorus compounds are also conceivable, but not only are there problems in terms of safety and environmental harmony, but especially when a phosphorus compound is added to a polyester resin, the heat resistance decreases due to plasticization, and the molded product of the phosphorus compound. Since bleeding to the surface occurs, it cannot be said to be a practically preferable technique.

  Therefore, the present inventor has focused on nitrogen compounds, particularly melamine, as non-halogen / non-phosphorus flame retardants used in polyester resins. The point of using nitrogen compounds, particularly melamine, as a flame retardant is disclosed in, for example, Patent Documents 1-4.

JP 54-112958 A Japanese Patent Publication No. 60-33850 Japanese Patent Publication No.59-50184 Japanese Examined Patent Publication No. 62-39174

By the way, since melamine starts decomposing | disassembling at 220-250 degreeC, it had the subject that a melamine decomposes | disassembles at the molding temperature of general polyester-type resin, such as PET and PBT, and a molding defect will be produced.
Further, simply adding melamine to a polyester-based resin is inferior in stress relaxation characteristics as compared with a vinyl chloride-based resin. For example, when used as a tape material, there is a problem that it is easily peeled off after winding.

  Accordingly, the present invention provides a flame retardant polyester resin composition comprising a polyester resin and melamine as a flame retardant, and the melamine is not decomposed during molding to cause defective molding, and vinyl chloride. It is intended to provide a new flame retardant polyester resin composition having the stress relaxation characteristics as described above.

  The present invention is a flame retardant polyester resin composition containing a mixture of a polyester resin (A), a melamine (B), and a phenoxy resin (C), and the polyester resin (A) is a polyvalent carboxylic acid. The first characteristic is that 50 to 90 mol% of terephthalic acid is contained as the acid component, and 70 to 100 mol% of 1,4-butanediol, ethylene glycol, and diethylene glycol are contained as the polyhydric alcohol component in total. The second feature is that the proportion of melamine (B) in the flame-retardant polyester resin composition is 10 to 60% by mass and the proportion of phenoxy resin (C) is 1 to 25% by mass. A flame-retardant polyester resin composition is proposed.

Polyester resin containing 50 to 90 mol% terephthalic acid as the polyvalent carboxylic acid component, and 70 to 100 mol% in total as the polyhydric alcohol component, 1,4-butanediol, ethylene glycol, and diethylene glycol (A) has a lower melting point than general polyester resins such as PET and PBT, and can be molded at a temperature lower than the temperature at which melamine decomposes. It can be eliminated. In addition, excellent flexibility and mechanical properties can be obtained.
Thus, by blending melamine (B) with a specific polyester resin (A) having excellent flexibility and mechanical properties, it has been studied in the past without impairing the inherent properties of the polyester resin. The addition amount is lower than that of the inorganic flame retardant, and excellent flame retardancy can be imparted.
Further, since the phenoxy resin is completely compatible with the specific polyester resin (A), the cohesive phenoxy resin can be finely dispersed in the polyester resin, and excellent stress relaxation characteristics can be obtained. . Moreover, since phenoxy resin has the property of being easily carbonized, the carbonization promoting effect of phenoxy resin and the combustion effect of melamine work synergistically, further improving flame retardancy while suppressing the amount of melamine compounded. Can be made.

  Hereinafter, a flame-retardant polyester-based resin composition (hereinafter referred to as “the present flame-retardant PEs resin composition”) as an example of an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the embodiments described below.

<This flame-retardant PEs resin composition>
The flame retardant PEs resin composition is a flame retardant polyester resin composition containing a mixture of a polyester resin (A), a melamine (B), and a phenoxy resin (C).

(Polyester resin (A))
The polyester-based resin (A) is a resin composition mainly composed of a polyester-based resin (a) which is a polycondensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol. It is a polyester-based resin containing 50 to 90 mol% of terephthalic acid as a monovalent carboxylic acid component and 70 to 100 mol in total of 1,4-butanediol, ethylene glycol, and diethylene glycol as a polyhydric alcohol component. Is preferred.
The resin composition mainly composed of the polyester resin (a) having such a composition has a lower melting point than general polyester resins such as PET and PBT, and a temperature lower than the temperature at which melamine decomposes. Since molding is possible, it is possible to eliminate the occurrence of molding defects due to decomposition of melamine during molding. In addition, excellent flexibility and mechanical properties can be obtained.
From this viewpoint, the polyester-based resin (a) preferably contains 55 mol% or more, particularly 60 mol% or more, more preferably 85 mol% or less, particularly 80 mol% or less, as the polyvalent carboxylic acid component. preferable. 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, the polyhydric alcohol component may include any one of 1,4-butanediol, ethylene glycol, and diethylene glycol, or may include two or more.

  In addition to terephthalic acid, the polyester resin (a) is, for example, one or two of isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid and other polyvalent carboxylic acids. It may contain more than seeds. In addition to 1,4-butanediol, ethylene glycol and diethylene glycol, for example, propylene glycol, 1,6-hexanediol, cyclohexanediol, polyoxylene glycol, polytetramethylene ether glycol and other polyvalent alcohols as polyhydric alcohols One kind or two or more kinds of alcohols may be contained.

  It is also possible to use a commercially available polyester resin as the polyester resin (a). For example, “Byron” series manufactured by Toyobo Co., Ltd., “Nichigo Polyester” series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and the like can be mentioned, and these can be used alone or in admixture of two or more.

Further, the polyester resin (A) may be a polyester resin mainly composed of a mixture of two or more kinds of polyester resins. Among them, a polyester resin containing isophthalic acid in a ratio of 5 mol% or more and less than 30 mol% in the polyvalent carboxylic acid component and ethylene glycol in a ratio of 0 mol% or more and less than 50 mol% in the polyhydric alcohol component ( a-1) and a polycarboxylic acid component containing isophthalic acid in a proportion of 30 mol% to 50 mol%, and a polyhydric alcohol component containing ethylene glycol in a proportion of 50 mol% to 100 mol%. A mixture with the polyester resin (a-2) is a particularly preferred example.
By using a mixture of the polyester resins (a-1) and (a-2) as the main component of the polyester resin (A), a resin composition having excellent mechanical properties and flexibility can be provided. In particular, by blending the polyester resin (a-2), flexibility, particularly easiness of elongation, can be enhanced.

At this time, the content of isophthalic acid in the polyvalent carboxylic acid component in the polyester resin (a-1) is more preferably 7 mol% or more, particularly preferably 10 mol% or more, and less than 25 mol%, particularly less than 20 mol%. More preferably.
Further, the content ratio of ethylene glycol in the polyhydric alcohol component in the polyester resin (a-1) is more preferably 5 mol% or more, particularly preferably 10 mol% or more, and less than 45 mol%, particularly less than 40 mol%. Is more preferable.

The content of isophthalic acid in the polyvalent 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. Further preferred.
Further, the content ratio of ethylene glycol in the polyhydric alcohol component in the polyester-based resin (a-2) is more preferably 55 mol% or more, particularly preferably 60 mol% or more, and 90 mol% or less, particularly 80 mol% or less. Is more preferable.

The mass average molecular weight of the polyester-based resin (A) (in the case of two types, the average) is preferably 10,000 to 300,000. If the mass average molecular weight of the polyester-based resin (A) is within such a range, flexibility can be obtained, and the melt viscosity is appropriate.
From this viewpoint, the mass average molecular weight of the polyester-based resin (A) is particularly preferably 20,000 or more, more preferably 30,000 or more, particularly 200,000 or less, especially 150,000 or less. Is more preferable.

The mass average molecular weight can be measured by the following method. The same applies to other resins.
Using gel permeation chromatography, measurement is made at a solvent chloroform, a solution concentration of 0.2 wt / vol%, a solution injection amount of 200 μL, a solvent flow rate of 1.0 ml / min, a solvent temperature of 40 ° C., and a mass average molecular weight in terms of polystyrene is obtained. Can be calculated. The mass average molecular weight of the standard polystyrene used in this case is 20000, 430000, 110000, 35000, 10000, 4000, 600.

  The glass transition temperature Tg of the polyester resin (A) is preferably -100 ° C to 40 ° C. When the Tg of the polyester resin (A) is within a temperature range, a flame retardant polyester resin composition excellent in mechanical properties such as flexibility and tensile strength can be prepared. From this viewpoint, the Tg of the polyester-based resin (A) is particularly preferably −90 ° C. or more, particularly preferably −80 ° C. or more, particularly preferably 35 ° C. or less, and particularly preferably 30 ° C. or less.

  The crystal melting temperature Tm of the polyester resin (A) is preferably 100 ° C to 190 ° C. When the Tm of the polyester resin (A) is within a temperature range, a flame retardant polyester resin composition excellent in mechanical properties such as flexibility and tensile strength can be prepared. From this viewpoint, the Tm of the polyester-based resin (A) is particularly preferably 105 ° C. or higher, particularly preferably 110 ° C. or higher, and is preferably 185 ° C. or lower, particularly 180 ° C. or lower.

  The crystal melting heat ΔHm of the polyester resin (A) is preferably 1 J / g to 30 J / g. If ΔHm of the polyester-based resin (A) is within a temperature range, a flame-retardant polyester-based resin composition having excellent mechanical properties such as flexibility and tensile strength can be prepared. From this viewpoint, ΔHm of the polyester-based resin (A) is particularly preferably 5 J / g or more, particularly preferably 10 J / g or more, particularly preferably 28 J / g or less, and particularly preferably 25 J / g or less.

(melamine)
Melamine is a kind of organic nitrogen compound having a triazine ring at the center of the structure, and examples thereof include 2,4,6-triamino-1,3,5-triazine. Since melamine generates nonflammable gas at the time of combustion, the flame retardant PEs resin composition can be made flame retardant. Melamine has a decomposition initiation temperature lower than that of melamine derivatives (for example, melamine cyanurate, melamine phosphate, etc.) and does not promote carbonization, so it is generally difficult to use as a flame retardant. However, when blended with the polyester resin (A) of the present invention, it can be melt-kneaded at a temperature lower than the decomposition start temperature of melamine, and melamine decomposes before decomposition of the resin during combustion. Thus, excellent flame retardancy can be imparted by the endothermic action during sublimation and the generation of inert gas.

The average particle size of melamine is preferably 10 μm or less, particularly preferably 0.5 μm to 10 μm. As long as the average particle size of melamine is within this range, melamine does not agglomerate and is uniformly dispersed in the resin composition, so that flame retardancy is not impaired without impairing the mechanical strength of the flame retardant PEs resin composition. Can be improved. From this point of view, the average particle size of melamine is particularly preferably 1.0 μm or more, particularly preferably 1.5 μm or more, particularly preferably 8.0 μm or less, and particularly preferably 6.0 μm or less.
The average particle diameter is a value calculated by using melamine as the equivalent circle diameter.

A surface treatment can be applied to melamine as long as the effects of the present invention are not impaired.
Specific examples of the surface treatment include surface treatment using a silane coupling agent such as epoxy silane, vinyl silane, methacryl silane, amino silane, isocyanate silane, titanate coupling agent, higher fatty acid and the like.
By treating melamine with these surface treatment agents, the dispersibility of melamine can be improved and the flame retardancy of the present flame retardant PEs resin composition can be further improved.

In addition, melamine and other flame retardants or flame retardant aids may be used in combination as long as the effects of the present invention are not impaired.
Specific examples of other flame retardants include, for example, phosphoric acid esters, phosphoric acid ester amides, condensed phosphoric acid esters, phosphazene compounds, phosphorus compounds such as polyphosphates, aluminum hydroxide, magnesium hydroxide, calcium aluminate water Examples thereof include metal hydroxides such as hydrates and tin oxide hydrates.
Specific examples of flame retardant aids include, for example, metal compounds such as zinc stannate, zinc borate, iron nitrate, copper nitrate, and sulfonic acid metal salts, silicone compounds such as dimethyl silicone, phenyl silicone, and fluorine silicone, polytetrafluoro Fluorine compounds such as ethylene can be mentioned.
By using these flame retardants and flame retardant aids in combination, the flame retardancy of the present flame retardant PEs resin composition can be further improved.

(Phenoxy resin)
The phenoxy resin is a resin obtained by a reaction between an aromatic dihydric phenol compound such as bisphenol A and epichlorohydrin.
Since the phenoxy resin is completely compatible with the specific polyester resin (A), the cohesive phenoxy resin can be finely dispersed in the polyester resin (A), resulting in excellent stress relaxation characteristics. Obtainable. Moreover, since the phenoxy resin has the property of being easily carbonized, it works synergistically with the flaming effect of melamine, further reducing the flame retardancy of the flame retardant PEs resin composition while suppressing the blending amount of melamine. Can be improved.

  Phenoxy resins used include hydroquinone, resorcin, 4,4'-bisphenol, 4,4'-dihydroxydiphenyl ether, bisphenol A, bisphenol F, and aromatic dihydroxy compounds such as 2,6-dihydroxynaphthalene, ethylene glycol diglycidyl One or more compounds selected from aliphatic dihydroxy compounds such as ether propylene glycol diglycidyl ether, neopentyl glycol, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Examples thereof include polyhydroxy polyether obtained by condensing with epichlorohydrin.

  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, PKFE manufactured by InChem. Among these, from the viewpoint of imparting flame retardancy, Epicoat (registered trademark) E4275 made by Japan Epoxy Resin Co., Ltd., whose main component is bisphenol F, is particularly preferable.

(Mixing ratio)
The blending ratio of melamine in the flame retardant PEs resin composition is preferably 10 to 60% by mass. If the blending ratio of melamine in the flame retardant PEs resin composition is 10% by mass or more, sufficient flame retardancy can be obtained, while if the blending ratio of melamine is 60% by mass or less, mechanical properties. Will not be damaged. From this viewpoint, the blending ratio of melamine in the flame retardant PEs resin composition is particularly preferably 20% by mass or more, and more preferably 30% by mass or more. Moreover, it is especially preferable that it is 50 mass% or less, and it is still more preferable that it is 40 mass% or less especially.

The blending ratio of the phenoxy resin in the flame retardant PEs resin composition is preferably 1 to 25% by mass. When the blending ratio of the phenoxy resin is within such a range, stress relaxation characteristics and flame retardancy can be improved. From this viewpoint, the proportion of the phenoxy resin in the flame retardant PEs resin composition is preferably 2% by mass or more, and more preferably 5% by mass or more. Moreover, it is preferable that it is 20 mass% or less, and it is still more preferable that it is 10 mass% or less especially.
In particular, when a tape is prepared from the flame retardant PEs resin composition, it is preferable to adjust the glass transition temperature Tg of the polyester resin (A) to 40 to 50 ° C. by blending a phenoxy resin.

(Other ingredients)
A carbodiimide compound may be blended with the flame retardant PEs resin composition in order to impart hydrolysis resistance. However, it is not necessary to mix.

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

  Specifically, for example, bis (dipropylphenyl) carbodiimide, poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropyl) Examples thereof include phenylene carbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), and the like. The carbodiimide compound is used alone or in combination of two or more.

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 this flame-retardant PEs resin composition. By mix | blending a carbodiimide compound in this range, the outstanding hydrolysis resistance can be provided, without reducing heat resistance.
From this viewpoint, the amount of the carbodiimide compound is more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, with respect to 100 parts by mass of the flame retardant PEs resin composition. Moreover, it is more preferable that it is 4 mass% or less, and it is preferable that it is 3 mass% or less especially.

  The flame retardant PEs resin composition may contain additives such as a heat stabilizer, an antioxidant, a UV absorber, a plasticizer, a nucleating agent, a light stabilizer, a pigment, and a dye as necessary. .

<Physical characteristics of the flame retardant PEs resin composition>
The flame-retardant PEs resin composition can have flame retardancy, flexibility, mechanical properties, and stress relaxation properties, and can be further prepared with heat resistance.
More specifically, regarding the flame retardancy, flame retardancy satisfying the VTM-0 standard can be obtained in the UL94 vertical combustion test defined by Underwriters Laboratories.
Regarding the mechanical properties, when the tensile strength at break is measured based on JIS C 2318, the tensile strength can be adjusted to 10 MPa or more, preferably 15 MPa or more.
Regarding the flexibility, when the tensile elongation at break is measured according to JIS C 2318, the tensile elongation can be adjusted to 10% or more, preferably 20% or more.
Regarding the stress relaxation characteristics, when the stress relaxation rate is measured based on JIS C 2318, the stress relaxation rate can be adjusted to 50% or more, preferably 55% or more.
Regarding heat resistance, when the crystal melting heat quantity ΔHm is measured based on JIS K7121, the crystal melting heat quantity (ΔHm) can be adjusted to 1 J / g or more, preferably 5 J / g or more.

<Uses of the present flame-retardant PEs resin composition>
The flame retardant PEs resin composition can be formed into a film, a sheet, a plate, an injection molded product, or the like.
Specifically, raw materials such as polyester resin (A), melamine (B) and phenoxy resin (C), and other resins and additives, if necessary, are directly mixed and put into an extruder or injection molding machine. Or a method in which the raw material is melt-mixed using a twin-screw extruder, extruded into a strand shape to create pellets, and then the pellets are put into an extruder or injection molding machine to be molded. be able to. In any method, it is necessary to consider a decrease in molecular weight due to hydrolysis of the polyester-based resin, and the latter is preferably selected for uniform mixing. Therefore, the latter manufacturing method will be described below.

Polyester resin (A), melamine (B), phenoxy resin (C), and other resins and additives as necessary are thoroughly dried to remove moisture, and then melt mixed using a twin screw extruder. The pellet is formed by extruding into a strand shape.
At this time, considering the composition ratio of the polyester resin (A), for example, the melting point changes depending on the content ratio of terephthalic acid, and the viscosity changes depending on the blending ratio of each raw material, the melt extrusion temperature is appropriately set. It is preferable to select. In consideration of the sublimation temperature of melamine, the molding temperature is preferably adjusted to a temperature range of 160 ° C. to 220 ° C., particularly less than 210 ° C.

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

  As film, sheet and plate molding methods, roll stretching, tenter stretching, tubular and inflation methods, as well as sheet and plate molding methods such as general T-die casting and pressing can be adopted. it can.

The molding method of the injection molded body is not particularly limited, and for example, an injection molding method such as a general injection molding method for a thermoplastic resin, a gas assist molding method, and an injection compression molding method can be employed.
In addition to the above methods, an in-mold molding method, a gas press molding method, a two-color molding method, a sandwich molding method, PUSH-PULL, SCORIM, or the like can also be employed according to other purposes.

Moreover, the laminated body can also be formed by providing one or more layers not containing a flame retardant on one side or both sides of the layer made of the flame retardant PEs resin composition.
At this time, the layer containing no flame retardant is not particularly limited. For example, in the case of imparting heat resistance, mechanical properties, and surface properties, a layer made of the stretched polyethylene terephthalate film or the like is formed. Is preferred. For the purpose of improving adhesiveness with other materials and using for adhesive tapes, etc., adhesive layer made of rubber, acrylic, vinyl ether or other solvent type or emulsion type adhesives Is preferably formed.
Under the present circumstances, it is preferable that the ratio of the thickness of the layer which consists of a flame-retardant polyester-type resin composition which occupies for the whole thickness of a laminated body is 20 to 95%. By setting the thickness ratio of the flame-retardant polyester resin composition within such a range, it is possible to provide a laminate that does not impair flame retardancy and mechanical properties. From this viewpoint, the ratio of the thickness of the layer composed of the flame-retardant polyester resin composition in the total thickness of the laminate is particularly preferably 30% or more, and particularly preferably 40% or more, and 80%. It is particularly preferable that the ratio is 70% or less.

  As a method of laminating the layer composed of the present flame retardant PEs resin composition and the layer not containing a flame retardant, the layers can be laminated by coextrusion, extrusion lamination, thermal lamination, dry lamination, or the like.

  In the case of co-extrusion, a laminate is formed by joining a plurality of layers through a feed block or a multi-manifold die using a plurality of extruders. In order to further impart heat resistance and mechanical strength to the laminate, the laminate obtained in the above step can be stretched uniaxially or biaxially using a roll method, a tenter method, a tubular method, or the like. .

  In the case of extrusion lamination, a layer made of a polyester resin (A) is extruded from a T die, I die, etc. using a single screw or twin screw extruder, and then a roll method, a tenter method, a tubular method, etc. To obtain a monolayer. Subsequently, a laminate can be obtained by laminating a layer containing no flame retardant on one side or both sides of the obtained layer.

  In the case of thermal lamination and dry lamination, a layer made of the polyester resin (A) is extruded from a T die, an I die or the like using a single screw or twin screw extruder to obtain a single layer body. Moreover, the layer which does not contain a flame retardant is produced using the same method. Subsequently, these layers are laminated by heating or by disposing an adhesive layer between the layers, whereby a laminate can be obtained.

Since this flame-retardant PEs resin composition has excellent flame retardancy, mechanical properties, and flexibility, it can be used for mobile phone parts, cable coating materials, packings, films and sheets for electrical insulation, flat cable materials, It can be widely used in fields such as home appliances such as damping materials, adhesive tape base materials, rolls, water shielding sheets, gaskets, anti-slip materials, wire clothing materials, and other building materials and industrial applications. In addition, since it does not contain a halogen compound or a phosphorus compound, it is possible to provide a material with excellent safety that does not cause problems such as environmental pollution.
Among these, since the flame-retardant PEs resin composition has excellent stress relaxation properties, it is particularly excellent as a substitute material for a so-called vinyl tape, particularly as a substitute material for a flame-retardant vinyl tape.

<Explanation of terms>
In the present invention, the expression “main component” includes the meaning of allowing other components to be contained within a range that does not hinder the function of the main component unless otherwise specified. Although the content ratio of the main component is not particularly specified, its component (when two or more components are main components, the total amount thereof) is 60% by mass or more, particularly 70% by mass or more in the composition. Of these, 90% by mass or more (including 100%) is preferable. For example, the mixture in the resin composition a preferably occupies 60% by mass or more, particularly 70% by mass or more, particularly 90% by mass or more (including 100%) in the resin composition a.

Further, in this specification, when “X to Y” (X and Y are arbitrary numbers) is described, it means “X or more and Y or less” unless otherwise specified, or “preferably larger than X” or The meaning of “preferably smaller than Y” is included.
In addition, when “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.

  In general, "film" refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, usually supplied in the form of a roll. (Japanese Industrial Standards JISK6900), “sheet” generally refers to a product that is thin by definition in JIS and whose thickness is small and flat instead of length and width. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, it includes “sheet” and is referred to as “sheet”. In some cases, “film” is included.

  Examples are shown below, but the present invention is not limited by these. In addition, the result shown in an Example evaluated by the following method.

(1) Flame retardance When the thickness is 200 μm or less, the sample for evaluation of length 200 mm × width 50 mm (thickness varies depending on each test piece), when the thickness exceeds 200 μm, length 127 mm × width 13 mm ( Underwriters Laboratories safety standard UL94 thin material vertical combustion test (when sample thickness is 200 μm or less) and UL94 vertical combustion test (sample thickness is 200 μm) Based on the above procedure, a combustion test is performed at a test count of 5 times, the state of combustion (especially the presence or absence of drops during combustion) is observed, and the combustion time (total combustion time of the test count of 5 times) Was measured.
In the UL94 vertical combustion test, samples with a thickness of 200 μm or less are judged on the basis of the UL94VTM criteria whether or not the VTM-0, 1 and 2 standards are satisfied. A product satisfying VTM-0 was evaluated as an acceptable product. For samples with a thickness exceeding 200 μm, whether or not the standards of VTM-0, 1, and 2 are satisfied is judged based on the UL94V criteria, and those that do not satisfy VTM-2 are evaluated as non-standard. Those satisfying −0 were evaluated as acceptable products.

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

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

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

a. The temperature was raised from 30 ° C. to 200 ° C. at a rate of 500 ° C./min, and then held at 200 ° C. for 2 minutes.
b. Next, the temperature drop was measured from 200 ° C. to 30 ° C. at a rate of 10 ° C./min.
c. Furthermore, the temperature rise measurement was performed from 30 ° C. to 200 ° C. at a rate of 10 ° C./min.

  The heat of crystal melting (ΔHm) was read from the thermogram obtained in the process of c.

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

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

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

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

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

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

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

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

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

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

Example 1
After dry blending (A) -1, (A) -3, (B) -1, and (C) -1 at a mixing mass ratio of 55: 20: 15: 5, 40 mmφ co-directional twin screw extrusion After kneading at 200 ° C. using a machine, it was extruded from a T-die and then rapidly cooled with a casting roll at about 40 ° C. to produce a sheet having a thickness of 100 μm. The obtained sheet was evaluated for flame retardancy, tensile strength, tensile elongation, and stress relaxation characteristics. The results are shown in Table 1.

(Example 2)
The same as Example 1 except that the mixing mass ratio of the polyester resins (A) -1, (A) -3, (B) -1, and (C) -1 was 45: 20: 30: 5. A sheet having a thickness of 100 μm was produced by this method. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 3)
The same as Example 1 except that the mixing mass ratio of the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 was 15: 20: 55: 5. A sheet having a thickness of 100 μm was produced by this method. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

Example 4
Example 1 After dry blending the polyester resins (A) -2, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 45: 20: 30: 5 A sheet having a thickness of 100 μm was produced in the same manner as described above. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 5)
After dry blending (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 65: 30: 5, a sheet having a thickness of 100 μm is produced in the same manner as in Example 1. did. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 6)
After dry blending the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 65: 30: 5, the same as in Example 1 A sheet having a thickness of 100 μm was prepared by the above method. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 7)
After dry blending the polyester resins (A) -4, (B) -1 and (C) -1 at a mixing mass ratio of 65: 30: 5, the thickness was 100 μm in the same manner as in Example 1. A sheet was produced. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 8)
After dry blending the polyester resins (A) -5, (B) -1 and (C) -1 at a mixing mass ratio of 65: 30: 5, the thickness was 100 μm in the same manner as in Example 1. A sheet was produced. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

Example 9
Example 1 After dry blending the polyester resins (A) -1, (A) -3, (B) -1, and (C) -1 at a mixing mass ratio of 48: 20: 30: 2 A sheet having a thickness of 100 μm was produced in the same manner as described above. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 10)
Example 1 After dry blending the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 40: 20: 30: 10 A sheet having a thickness of 100 μm was produced in the same manner as described above. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 11)
Example 1 After dry blending the polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 at a mixing mass ratio of 30: 20: 30: 20 A sheet having a thickness of 100 μm was produced in the same manner as described above. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

Example 12
Example 1 After dry blending the polyester resins (A) -1, (A) -3, (B) -1, and (C) -2 at a mixing mass ratio of 40: 20: 30: 10 A sheet having a thickness of 100 μm was produced in the same manner as described above. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

(Example 13)
Similarly to Example 2, polyester resins (A) -1, (A) -3, (B) -1 and (C) -1 were blended at a mixing mass ratio of 45: 20: 30: 5, and Mitsubishi. It was compounded at 190 ° C. using a heavy industry 40 mmφ small-sized co-directional twin screw extruder to form a pellet. A plate material having a length of 250 mm, a width of 200 mm and a thickness of 1 mm was injection molded from the obtained pellets using an injection molding machine IS50E (screw diameter: 25 mm) manufactured by Toshiba Machine. The main molding conditions are as follows.
1) Temperature conditions: Cylinder temperature (190 ° C) Mold temperature (30 ° C)
2) Injection conditions: Injection pressure (115 MPa) Holding pressure (55 MPa)
3) Measurement conditions: Screw rotation speed (65 rpm) Back pressure (15 MPa)
A sample for evaluation is cut out from the obtained molded product, and the results of the same evaluation as in Example 1 are shown in Table 1.

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

(Comparative Example 2)
Example 1 After dry blending polyester resins (A) -1, (A) -3, (B) -1, and (C) -1 at a mixing mass ratio of 70: 20: 5: 5, Example 1 A sheet having a thickness of 100 μm was produced in the same manner as described above. Table 1 shows the results of the same evaluation as in Example 1 for the obtained sheet.

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

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

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

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

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

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

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

It is confirmed that the stress relaxation property of the polyester resin (A) can be improved by adding the phenoxy resin (C) to the polyester resin (A), and the flame retardancy can be further improved. did it.
The proportion of the phenoxy resin (C) is preferably 1 to 25% by mass of the flame retardant polyester resin composition, particularly 2% by mass or more, more preferably 5% by mass or more, and more preferably 20% by mass. In the following, it was found that 10% by mass or less is more preferable.

In addition, melamine can be made flame retardant by blending it with polyester resin (A), whereas melamine derivatives such as melamine cyanurate and melamine polyphosphate are specific polyester resins (A). The result that can not be flame retardant.
Melamine is generally difficult to use as a flame retardant, but it has been found that it can be used as a flame retardant for certain polyester resins. That is, from the results of Table 1, the polyester resin (A) -6 does not function as a flame retardant, whereas the polyester resins (A) -1 to (A) -5 function as a flame retardant. I understood that.
The proportion of melamine (B) is preferably 10 to 60% by mass of the flame retardant polyester resin composition, particularly 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or less. In particular, it was found that 40% by mass or less is more preferable.

Claims (4)

It is a flame retardant polyester resin composition containing a mixture of polyester resin (A), melamine (B), and phenoxy resin (C),
The polyester-based resin (A) contains 50 to 90 mol% of terephthalic acid as the polyvalent carboxylic acid component, and 70 in total of 1,4-butanediol, ethylene glycol, and diethylene glycol as the polyhydric alcohol component. The first feature is to contain ~ 100 mol%,
The second feature is that the ratio of melamine (B) in the flame-retardant polyester resin composition is 10 to 60% by mass and the ratio of phenoxy resin (C) is 1 to 25% by mass. A flammable polyester resin composition.   The polyester resin (A) contains isophthalic acid in a proportion of 5 mol% or more and less than 30 mol% in the polyvalent carboxylic acid component, and ethylene glycol in the polyhydric alcohol component in a proportion of 0 mol% or more and less than 50 mol%. The polyester-based resin (a-1) and the polycarboxylic acid component contain isophthalic acid in a proportion of 30 mol% or more and 50 mol% or less, and the polyhydric alcohol component contains ethylene glycol in an amount of 50 mol% or more and 100 mol%. It is a mixture with the polyester-type resin (a-2) contained in the following ratios, The flame-retardant polyester-type resin composition of Claim 1 characterized by the above-mentioned.   The flame retardant polyester resin composition according to claim 1 or 2, wherein an average particle size of melamine is 10 µm or less.   The molded object which consists of a flame-retardant polyester-type resin composition in any one of Claims 1-3.