JP2015052038A - Flame retardant polyester resin composition - Google Patents

Abstract

【選択図】 図１PROBLEM TO BE SOLVED: To provide a flame retardant polyester-based resin composition that can highly reduce the environmental load and cost during production and can be usefully used in various applications requiring flame retardancy.
SOLUTION: A flame-retardant polyester resin composition containing a recovered polyester component and containing 0.20% by weight or more of a phosphorus element, and a phosphorus-containing compound represented by the following formula (1) It is preferable that intrinsic viscosity is 0.45 dl / g or more.
[Figure 1]

[Selection] Figure 1

Description

  The present invention relates to a flame retardant polyester resin composition. More specifically, the present invention relates to a flame retardant polyester resin composition capable of reducing environmental burden and cost during production.

  Biaxially stretched polyester film excels in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, gas barrier properties, chemical resistance, etc., packaging materials, electrical insulation materials, metal deposition materials, plate making materials, It is used in many applications such as magnetic recording materials, display materials, transfer materials, and window paste materials.

  With the recent increase in heat generation due to downsizing and higher efficiency of personal computers and mobile phones, the polyester film for labels used in the batteries of these devices requires a thin film on the label from the viewpoint of miniaturization, and heat generation. From the viewpoint of fire prevention from the origin, there is an increasing demand for flame-retardant labels. In general, as an indicator of flame retardancy, certification under the standard UL94 of UNDERWRITERS LABORATORIES is often used.

  As a flame-retarding technique for polyester films, for example, as disclosed in Patent Documents 1 to 4, various phosphorus-containing compounds, halogen-containing compounds, metal compounds, etc. are added or mixed or copolymerized melt extrusion molding is proposed. Has been.

  However, in order to impart sufficient flame retardancy to the film, it is necessary to add a large amount of flame retardant compound, so that the thermal stability and mechanical strength are lowered. In particular, when an organic halogen compound and antimony trioxide are used in combination, good flame retardancy can be obtained. On the other hand, the above-described drawbacks are remarkable, and a gel compound is generated when these compounds are melted and kneaded.

  The polyester film is generally obtained by stretching an amorphous polyester sheet that has been melt-extruded from a die and rapidly cooled and solidified. And at the time of manufacture of a polyester film, the edge part of a polyester sheet becomes thick by the neck-in phenomenon at the time of extrusion, and is used as a biting allowance of a clip. When commercialized, the end of the polyester film is cut and separated as an ear film. Further, when the master roll from which the ear portion is removed is slit to the product size, the excess slit ear is cut and separated.

  Patent Document 5 is an invention relating to a flame-retardant polyester film having a specific phosphorus structure. It is recognized that the polyester film has flame retardancy. However, since the above-mentioned ear film and excessive slit ear are not utilized, it is not preferable from the viewpoint of environmental load and cost.

Japanese Patent Publication No.51-19858 Japanese Patent Publication No. 55-41610 Japanese Examined Patent Publication No. 62-61235 Japanese Patent Laid-Open No. 62-132955 JP 2012-184399 A

  This invention is made | formed in view of the said situation, The solution subject is to provide the flame-retardant polyester-type resin composition which can reduce the environmental impact at the time of manufacture, and cost.

  As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be easily solved by adopting a specific configuration, and the present invention has been completed.

  That is, the gist of the present invention resides in a flame retardant polyester resin composition containing a recovered polyester component and containing 0.20% by weight or more of a phosphorus element.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the polyester-type resin composition which has the flame retardance which can reduce the environmental burden at the time of manufacture, and reduction of cost. The industrial value of the present invention is high.

Combustion test equipment

  The polyester resin used in the resin composition of the present invention is not particularly limited, and is mainly a polyester obtained using aromatic dicarboxylic acid or its ester and glycol as main starting materials, and has a repeating structure. It refers to a polyester in which 60% or more of the units have ethylene terephthalate units or ethylene-2,6-naphthalate units. And if it is the conditions which do not deviate from said range, the other 3rd component may be contained. For example, a mixture of a resin compatible with a polyester-based resin such as polycarbonate can be used.

  Examples of the aromatic dicarboxylic acid component include terephthalic acid, dimethyl terephthalate, and 2,6-naphthalenedicarboxylic acid, for example, isophthalic acid, phthalic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxyethoxy) Benzoic acid etc.) can be used. In particular, terephthalic acid or dimethyl terephthalate is preferably used.

  As an example of a glycol component, 1 type, or 2 or more types, such as diethylene glycol, propylene glycol, butylene glycol, can be used other than ethylene glycol, for example. In particular, it is preferable to use ethylene glycol.

  The amount of phosphorus element (% by weight) in the flame-retardant polyester resin composition of the present invention is determined by ICP described later. The range of the amount of phosphorus element is 0.20% by weight or more, preferably 0.50% by weight or more, more preferably 0.80% by weight or more, and particularly preferably 1.0% by weight or more. When the phosphorus element amount is less than 0.20% by weight, for example, the flame retardancy after processing into a polyester film becomes unstable.

  The upper limit of the amount of phosphorus element in the flame retardant polyester resin composition is not particularly set, but is preferably 4.00% by weight, more preferably 3.00% by weight, further preferably 2.00% by weight, and 1.50. Weight percent is particularly preferred. When the amount of phosphorus element is higher than 4.00% by weight, compounds having a low softening point other than the polyester component occupy a relatively large ratio. As a result, for example, when forming a polyester film, when a flame retardant polyester resin composition is dropped onto an extruder screw from a feeder, the cylinder around the dropping portion is hot, so the polyester resin composition Melting starts from the surface of the pellets, and adhesion between the polyester resin composition pellets occurs around the dropping part, and bridging occurs, so that there is a tendency that stable film formation of the polyester film becomes difficult.

  As the phosphorus-based flame retardant used in the flame-retardant polyester resin composition of the present invention, it is preferable to use a phosphorus-containing compound represented by the following chemical formula (1).

  The organophosphorus compound represented by the chemical formula (1) contains a phosphorus atom in the molecule, and the lower limit of the repeating unit of n is 4, preferably 8, and more preferably 12. If the repeating unit is less than 4, the mechanical strength may be reduced due to volatilization of the organophosphorus compound during film formation and inhibition of crystallization of the polyester resin. Furthermore, due to bleeding out of the organic phosphorus compound, a sticky component is generated on the surface of the polyester pellet, which is not preferable from the viewpoint of adhesion. On the other hand, the upper limit of the repeating unit of n is not particularly specified, but it is considered that dispersibility of the compound (1) in the resin is inhibited by excessively increasing the molecular weight. In addition, the synthesis method (production example) of compound (1) will be described later.

  The intrinsic viscosity of the flame retardant polyester resin composition of the present invention is preferably 0.45 dl / g or more, more preferably 0.55 dl / g or more, still more preferably 0.65 dl / g or more, and 0.80 dl / g. The above is particularly preferable, and 0.95 dl / g or more is most preferable. When the intrinsic viscosity of the flame retardant polyester resin composition is less than 0.45 dl / g, the polyester film using the recovered flame retardant polyester resin composition tends to break.

  Usually, a polyester film is obtained by stretching an amorphous polyester sheet that has been melt-extruded from a die and rapidly cooled and solidified. And at the time of manufacture of a polyester film, the edge part of a polyester sheet becomes thick by the neck-in phenomenon at the time of extrusion, and is used as a biting allowance of a clip. When commercialized, the end of the polyester film is cut and separated as an ear film. Further, when the master roll from which the ear portion is removed is slit to the product size, the excess slit ear is cut and separated.

Examples of the flame-retardant polyester resin composition of the present invention include, but are not limited to, the following.
(1) Polyester obtained by flaking the tip of a flame-retardant polyester film obtained only with a virgin resin (2) Polyester obtained by solid-phase polymerization of the above (1) to increase the IV (3) The above (1 ) Addition of flame retardant to polyester (4) Melt mixed polyester (4) Recycled PET bottles are pulverized and melted into chips, solid phase polymerized PET and flame retardant polyester (5) Polyester containing no flame retardant Polyester obtained by melt-mixing a flame-retardant polyester with a solid phase polymerized chip after flaking the film ear

  More specifically, the flakes obtained by pulverizing the ear film cut and separated from the flame-retardant polyester film having a phosphorus element amount of 0.20% by weight or more, the flakes obtained by pulverizing the slit ears, and the flakes are extruded. Including pelletized material melt-extruded by a machine. Also, in order to improve the intrinsic viscosity (dl / g), flakes and slit ears obtained by pulverizing the ear film cut and separated from the flame retardant polyester film having a phosphorus element amount of 0.20% by weight or more are crushed. The pelletized product obtained by melting and extruding the flaked product obtained by an extruder is preferably a recovered flame-retardant polyester resin composition having a high molecular weight by solid phase polymerization.

  In addition, since the flame retardant polyester resin composition includes a flame retardant having a low softening point, the polyester is used under conditions of less than 200 ° C. in order to prevent adhesion between the polyester pellets during solid phase polymerization. A method of obtaining a recovered flame-retardant polyester resin composition having a high molecular weight by solid-phase polymerization at a set temperature of 210 ° C. or higher after the pellets are sufficiently crystallized is preferable. The crystallization temperature is more preferably less than 190 ° C, and even more preferably less than 180 ° C.

  The flame-retardant polyester resin composition of the present invention also includes a resin composition obtained by melt-mixing and pelletizing a flaked product obtained by the above-described method and a phosphorus compound represented by the chemical formula (1). .

  The flame-retardant polyester-based resin composition of the present invention is a polyester chip obtained by melt-mixing a pulverized product of a commercially available polyethylene terephthalate bottle, and the polyester chip is made into a high molecular weight by solid phase polymerization, and Also included is a resin composition obtained by melting and mixing with a phosphorus compound represented by the chemical formula (1).

  The flame-retardant polyester resin composition of the present invention is a polyester chip obtained by melt-mixing a pulverized polyethylene terephthalate film that does not contain a flame retardant, and the polyester chip is made high molecular weight by solid phase polymerization. Also included is a resin composition obtained by melting and mixing a resin and a phosphorus compound represented by the chemical formula (1).

  In addition, the flame-retardant tree polyester resin of the present invention has an antistatic agent, an antioxidant, an ultraviolet absorber, an antifogging agent, a cross-linking agent, a plasticizer, an antiblocking agent, and a colorant, as long as the properties are not affected. Agents and pigments may be contained.

  In the flame-retardant polyester film using the recovered flame-retardant polyester resin of the present invention, the content of the recovered flame-retardant polyester resin is preferably 5.0% by weight or more, preferably 10.0% by weight as the polyester raw material to be used. % Or more, more preferably 15.0% by weight or more, particularly preferably 20.0% by weight or more, and most preferably 25.0% by weight or more. If the content of the flame retardant polyester resin is less than 5.0% by weight, it may not be preferable from the viewpoint of environmental load and cost.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The physical property measurement method used in the present invention is shown below.

(1) Amount of phosphorus element (wt%)
ICP: Varian Tech. The amount (% by weight) of phosphorus in the polyester sample was determined by acid decomposition with nitric acid using ICP-AES manufactured by the company.

(2) Intrinsic viscosity (dl / g)
A polyester sample of 0.5 g was dissolved in a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio), and the flow time of a solution having a concentration of 1.0 (g / dl) was measured using a capillary viscometer, In addition, the flow-down time of only the solvent was measured, and the intrinsic viscosity was calculated from the time ratio using the Huggins formula. At that time, the Huggins constant was assumed to be 0.33.

(3) Film-forming properties Assuming continuous production, from the frequency of product breakage, from the production of unstretched sheets to longitudinal stretching and lateral stretching of unstretched sheets and winding up as rolls, the following three rank criteria Judgment was evaluated.
○: Frequency of one film break is 10 minutes or more. Δ: Film break occurs once in 5 minutes or more and less than 10 minutes. ×: Film break occurs once or more in less than 5 minutes.

(4) Flame retardancy 4-1 Preparation of test piece As a film test piece, cut into 200 mm x 50 mm, and place a marked line across the width of the sample at 125 mm from one end (lower part) of the sample. The sample longitudinal axis is tightly wound around the mandrel with a diameter of 12.7 mm so that a 125 mm line is exposed to the outside and becomes a rolled cylinder with a length of 200 mm. The edge that protrudes outside the sample is fixed with an adhesive tape between 75 mm above the 125 mm mark (upper part of the cylinder). Then pull out the mandrel.

4-2 Conditioning The test piece obtained above is pretreated at 23 ° C. and 50% relative humidity for 48 hours.

4-3 Combustion test procedure 4-3-1 Fixation of test piece With the vertical axis of the sample vertical, fix it with a clamp with a strong spring at the position of the upper end length of 6 mm, and close the upper end of the tube during the test. Avoid the chimney effect. The lower end of the sample should be 300 mm above one horizontal 0.05 g defatted 100% cotton (50 mm × 50 mm) with a maximum thickness of 6 mm. See FIG.

4-3-2 Adjusting the burner Adjust the burner so that a blue flame with a height of 20 mm appears from the burner. In order to put out the flame, the gas supply and the air inlet of the burner are adjusted so that the yellow flame with a yellow tip of 20 mm comes out. Then increase the air supply until the yellow tip just disappears. Measure the flame height again and readjust as necessary. In addition, the methane gas supply to a burner adjusts a flow volume by the method according to ASTMD5207.

4-3-3 Flame contact for the first time The flame is centered on the center point of the lower end of the sample, and the tip of the burner is 10 mm below that point at the lower end of the sample. Continue for 3 seconds at a distance. However, the burner is moved in response to any change in the length or position of the sample. If a molten or fuming substance drips during flame contact, tilt the burner angle up to 45 degrees, just below the sample to prevent the substance from falling into the burner tube. Move from. However, the interval between the center of the tip of the burner and the remaining portion of the sample must be kept 10 mm ± 1 mm during that time. When the sample has an indirect flame for 3 seconds, the burner is immediately moved away from the sample at a rate of about 300 mm at a rate of at least 150 mm per second, and at the same time, the after flame time t ₁ is started to be measured in seconds by the timing device. And it records the _{t 1.}

4-4-4 Second flame contact When the after flame of the sample is extinguished (even if the burner is not completely removed to a distance of 150 mm from the sample), immediately bring the burner under the sample. Then, a burner is held at a location 10 mm ± 1 mm away from the rest of the sample. However, if necessary, move the burner so that the natural behavior of the fallen object can be confirmed without any obstructions. After this sample 3 seconds flame application, immediately away at least 150mm at a speed of about 300 mm, starts weighing the remaining flame time t ₂ seconds by a timing device at the same time.

4-5 Flame Retardancy Evaluation Criteria The test is performed on the five test pieces according to the procedure described in Section 4-3. The evaluation with the lowest standard among the five samples was taken as the evaluation value of the sample.
Good: a remaining flame time of the specimen t ₁ or t ₂ is less than 10 seconds, and the sample is not afterflame to 125mm marked line, and impossible cotton by smoke producing materials or droppings does not ignite: remaining flame time of the specimen t ₁ or t ₂ is at least 10 seconds, or article to afterflame to 125mm marked line, or cotton by smoke substance or droppings is ignited

  In order to further clarify the present invention, phosphorus-containing compounds (chemical formula (1)) used in the following Examples and Comparative Examples, and a method for producing a polyester raw material are as follows. In the examples, “%” represents “% by weight” unless otherwise specified.

<< Flame retardant A1: Phosphorus-containing compound (Chemical formula (1)) >>
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (the following chemical formula (2)) was added to a 3 L glass flask equipped with a stirrer, thermometer, gas inlet, and distillation port. ) 7.8 mol and 25.97 mol of ethylene glycol were added and the flask was heated until the temperature of the contents reached 100 ° C. to dissolve the components. Next, 7.96 mol of itaconic acid was added with stirring, and the flask was heated from the distillation port through a vacuum device in a vacuum state of 30 Torr to bring the contents to a boil. At this point, the produced water was removed by adjusting the distillation rate of the distillation port. Furthermore, while maintaining the boiling state of the contents, the temperature in the flask was raised, and the degree of vacuum was also lowered accordingly. As a breakdown, it took 4 hours for the temperature of the contents to reach 185 ° C., and the degree of vacuum at this point was 430 Torr. Further, the heating was continued, and finally the contents were heated until the temperature reached 200 ° C. After confirming this point, nitrogen gas was blown into the reactor to return the flask to normal pressure. The reaction mixture is an ethylene glycol solution of the following chemical formula (3). Moreover, the solid compound of the following chemical formula (3) can be purified by removing ethylene glycol under reduced pressure.

Subsequently, 130 g of ethylene glycol containing 0.33 g of antimony trioxide (Sb ₂ O ₃ ) and zinc acetate dihydrate [(AcO) ₂ Zn · 2H ₂ O] was added into the flask. The inside of the flask was maintained at 200 ° C., and the degree of vacuum was gradually increased to obtain a vacuum state of 1 Torr or less. Furthermore, the temperature of the content was raised to 220 ° C., and the point at which the distillation of ethylene glycol was extremely reduced was determined as the reaction end point. After confirming this point, the flame retardant A1 represented by the chemical formula (1), which is a yellowish transparent glassy solid, is obtained by solidifying the contents in a SUS container while pressurizing the contents with nitrogen gas. It was.

  By repeating the above operation, the necessary amount of the flame retardant A1 represented by the chemical formula (1) to be added in Examples and Comparative Examples described later was secured.

  Regarding the flame retardant A1 represented by the chemical formula (1), the weight average molecular weight (Mw) was 6,800 from GPC analysis of the product. In the analysis, a peak in a low molecular weight region, which was estimated to be an acid anhydride of a compound represented by the following chemical formula (4) or a cyclic ester of compound (4) and ethylene glycol, was also observed. Therefore, it can be said that the average value of n of the flame retardant A1 represented by the chemical formula (1) corresponds to 18.1. ICP measurement showed that the phosphorus element content (% by weight) was 8.31.

<< Flame Retardant A2: Phosphorus-containing compound (Chemical Formula (3)) >>
The phosphorus-containing compound represented by the chemical formula (3), that is, the compound of n = 1 in the chemical formula (1) obtained during the production of the flame retardant A1 is referred to as a flame retardant A2.

≪Production of polyester raw material (1) ≫
100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol are used as starting materials, 0.02 part of magnesium acetate tetrahydrate is taken as a catalyst in the reactor, the reaction start temperature is 150 ° C., and the methanol is gradually distilled off. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. After adding 0.03 part of ethyl acid phosphate to this reaction mixture, it moved to the polycondensation tank, added 0.04 part of antimony trioxide, and performed polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped when the intrinsic viscosity (dl / g) was 0.63 due to a change in the stirring power of the reaction vessel, the polymer was discharged under nitrogen pressure, extracted into a strand shape, The polyester (1) was produced by cutting with a cutter.

≪Manufacture of polyester raw material (2) ≫
The polyester resin (1) was used as a starting material, and solid phase polymerization was performed at 220 ° C. under vacuum to obtain a polyester (2) in a pellet state. The intrinsic viscosity (dl / g) of the obtained polyester was 0.85.

≪Production of polyester raw material (3) ≫
100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol are used as starting materials, and tetra-n-butyl titanate is obtained as a catalyst. The amount of titanium atoms per 1 ton of polyester resin is 5 g / resin t. In the reactor, the reaction start temperature was 150 ° C., and the reaction temperature was gradually increased as methanol was distilled off. After 4 hours, the transesterification reaction was substantially terminated. The reaction mixture was transferred to a polycondensation tank and the average particle size 2. An ethylene glycol slurry of 5 μm silica particles was added so that the content of the particles with respect to the polyester was 3.0% by weight, and a polycondensation reaction was performed for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.60 due to a change in stirring power of the reaction vessel, and the polymer was discharged under nitrogen pressure to obtain a polyester raw material (3). The intrinsic viscosity (dl / g) was 0.64.

≪Manufacture of polyester raw material (4) ≫
100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol are used as starting materials, 0.02 part of magnesium acetate tetrahydrate is taken as a catalyst in the reactor, the reaction start temperature is 150 ° C., and the methanol is gradually distilled off. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. After adding 0.03 part of ethyl acid phosphate to this reaction mixture, it was transferred to a polycondensation tank, 0.04 part of antimony trioxide and an ethylene glycol slurry of synthetic calcium carbonate particles having an average particle diameter of 0.8 μm were added to the particles. It added so that content with respect to polyester might be 1 weight%, and polycondensation reaction was performed for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped when the intrinsic viscosity (dl / g) was 0.63 due to a change in the stirring power of the reaction vessel, the polymer was discharged under nitrogen pressure, extracted into a strand shape, The polyester (4) was produced by cutting with a cutter.

≪Manufacture of polyester raw material (5) ≫
The flame retardant resin composition was prepared by kneading and extruding 35% by weight of the flame retardant A1 produced by the above-mentioned method and 65% by weight of the polyester (2) with a twin-screw kneader with a vent set to 290 ° C. Pellets were obtained. The intrinsic viscosity (dl / g) of the obtained polyester was 0.45.

≪Production of polyester raw material (6) ≫
Polyester obtained by washing and drying a recyclable polyethylene terephthalate bottle, crushing, and re-pelleting through a re-melting process was subjected to high molecular weight polymerization at 220 ° C. under vacuum to obtain a polyester (6) in the form of pellets. . The intrinsic viscosity (dl / g) of the obtained polyester was 1.10.

Example 1:
Using the polyester raw material (2), polyester raw material (3), and polyester (5) mixed at a ratio of 55.0: 2.5: 42.5 as a raw material, using a twin screw extruder with a vent of 90 mm in diameter , Discharge amount: 450 kg / hr, cylinder temperature: melt-extruded at 290 ° C., the amorphous polyester sheet flowing out from the die was rapidly cooled on a casting drum set to a surface temperature of 40 ° C. using an electrostatic application adhesion method Solidified to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer.

  The obtained pulverized product is supplied to a single screw extruder after drying, and the polyester pelletized after melt extrusion in a 290 ° C. environment is designated as a recovered flame retardant polyester resin composition (1). The intrinsic viscosity (dl / g) of the obtained polyester was 0.45. Table 1 shows the intrinsic viscosity of the recovered flame-retardant polyester resin composition (1) and the phosphorus element content obtained by ICP.

  The polyester raw material (2), the polyester raw material (3), the polyester (5), and the recovered flame retardant polyester resin composition (1) are in a ratio of 44.0: 2.0: 34.0: 20.0. The mixed polyester is used as a raw material and melted and extruded at a discharge rate of 450 kg / hr and a cylinder temperature of 290 ° C. with a vented twin screw extruder having a diameter of 90 mm. Was used to quench and solidify on a casting drum whose surface temperature was set to 40 ° C. to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer and stored for recovered polyester.

Example 2:
The recovered flame-retardant polyester resin composition (1) obtained in Example 1 was crystallized in an environment of 180 ° C. over 12 hours. The crystallized product was subjected to high molecular weight polymerization by solid phase polymerization at 215 ° C. under vacuum for 12 hours to obtain a pellet-shaped recovered flame-retardant polyester resin composition (2). The intrinsic viscosity (dl / g) of the obtained polyester was 1.01.

  The polyester raw material (2), the polyester raw material (3), the polyester (5), and the recovered flame-retardant polyester resin composition (2) are in a ratio of 44.0: 2.0: 34.0: 20.0. The mixed polyester is used as a raw material and melted and extruded at a discharge rate of 450 kg / hr and a cylinder temperature of 290 ° C. with a vented twin screw extruder having a diameter of 90 mm. Was used to quench and solidify on a casting drum whose surface temperature was set to 40 ° C. to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer and stored for recovered polyester.

Example 3:
Using the polyester raw material (2), the polyester raw material (3), and the polyester (5) mixed at a ratio of 76.2: 2.5: 21.3 as a raw material, using a vented twin screw extruder with a diameter of 90 mm , Discharge amount: 450 kg / hr, cylinder temperature: melt-extruded at 290 ° C., the amorphous polyester sheet flowing out from the die was rapidly cooled on a casting drum set to a surface temperature of 40 ° C. using an electrostatic application adhesion method Solidified to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a master roll of a polyester film having a thickness of 150 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer.

  The obtained pulverized product is dried and then supplied to a single screw extruder. After the melt extrusion in a 290 ° C. environment, the pelletized polyester is designated as a recovered flame-retardant polyester resin composition (3). The intrinsic viscosity (dl / g) of the obtained polyester was 0.58. Table 1 shows the intrinsic viscosity of the recovered flame-retardant polyester resin composition (3) and the phosphorus element content obtained by ICP.

  Polyester raw material (2), polyester raw material (3), polyester raw material (5), and recovered flame retardant polyester resin composition (3) in a ratio of 61.0: 2.0: 17.0: 20.0 The polyester blended in the above is used as a raw material, and the discharge rate: 450 kg / hr, cylinder temperature: 290 ° C is melt-extruded by a twin-screw extruder with a vent of 90 mm, and an amorphous polyester sheet flowing out from the die is electrostatically applied. An unstretched single layer sheet was obtained by quenching and solidifying on a casting drum having a surface temperature set to 40 ° C. using an adhesion method. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a master roll of a polyester film having a thickness of 150 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer and stored for recovered polyester.

Example 4:
Recovered flame retardant by kneading and extruding 35% by weight of flame retardant A1 produced by the above method and 65% by weight of polyester raw material (6) with a biaxial kneader with a vent set to 290 ° C. A pellet of the polyester resin composition (4) was obtained. The intrinsic viscosity (dl / g) of the obtained polyester was 0.50. Table 1 shows the intrinsic viscosity of the recovered flame-retardant polyester resin composition (4) and the phosphorus element content obtained by ICP.

  Polyester raw material (3), polyester raw material (6), recovered flame retardant polyester resin composition (4) mixed in a ratio of 2.5: 54.5: 43.0 as a raw material, and a diameter of 90 mm Using a twin-screw extruder with a vent, the discharge rate: 450 kg / hr, cylinder temperature: 290 ° C., melt-extruded, and the amorphous polyester sheet flowing out from the die was brought to a surface temperature of 40 ° C. using an electrostatic application adhesion method. It was rapidly cooled and solidified on the set casting drum to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer and stored for recovered polyester.

Example 5:
81% by weight of the polyester raw material (1) and 19% by weight of the polyester raw material (4) are mixed, supplied to a vented twin screw extruder, melt extruded at 290 ° C., and then subjected to surface temperature using an electrostatic application adhesion method. Was cooled and solidified on a cooling roll set at 40 ° C. to obtain an unstretched sheet. Next, the film was stretched 2.8 times in the longitudinal direction at 100 ° C., then subjected to a preheating step in a tenter and subjected to a transverse stretching of 5.1 times at 120 ° C., followed by heat treatment at 220 ° C. for 10 seconds, At 180 ° C., 4% relaxation was added in the width direction to obtain a master roll of a polyester film having a total thickness of 38 μm and a width of 2000 mm.

  When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film.

  A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. At the time of this slitting, cutting and separation were performed as the surplus slit ears generated.

  The cut-separated ear film and slit ear were pulverized by a pulverizer. The obtained pulverized product is dried and then supplied to a single screw extruder and melt-extruded in a 290 ° C. environment to obtain a polyester chip. The intrinsic viscosity (dl / g) of the polyester chip was 0.55.

  The above-mentioned polyester chip having an intrinsic viscosity (dl / g) of 0.55 was subjected to high molecular weight by solid phase polymerization at 220 ° C. under vacuum. The intrinsic viscosity (dl / g) of the obtained polyester was 1.12.

  65% by weight of the above-mentioned polyester chip having an intrinsic viscosity (dl / g) of 1.12, 35% by weight of the flame retardant A1 produced by the above method, and biaxial kneading with a vent set to 290 ° C. It knead | mixed and extruded with the machine and the pellet of the flame-retardant resin composition was obtained. The intrinsic viscosity (dl / g) of the obtained polyester was 0.51. Let the said polyester be the collection | recovery flame-retardant polyester-type resin composition (5). Table 1 shows the intrinsic viscosity of the recovered flame-retardant polyester resin composition (5) and the phosphorus element content obtained by ICP. In the table, “Raw material ratio for production of recovered flame retardant polyester resin composition” is polyester raw material (1): polyester raw material (4): flame retardant A1 = 52.7: 12.4: 35.0 , And the value obtained by calculation.

  Polyester raw material (3), polyester raw material (6), recovered flame retardant polyester resin composition (5) mixed in a ratio of 2.5: 54.5: 43.0 as a raw material, and a diameter of 90 mm Using a twin-screw extruder with a vent, the discharge rate: 450 kg / hr, cylinder temperature: 290 ° C., melt-extruded, and the amorphous polyester sheet flowing out from the die was brought to a surface temperature of 40 ° C. using an electrostatic application adhesion method. It was rapidly cooled and solidified on the set casting drum to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer and stored for recovered polyester.

Example 6:
35% by weight of flame retardant A2 produced by the above method and 65% by weight of polyester (6) were conveyed from a feeder and kneaded and extruded in a twin-screw kneader with a vent set to 290 ° C. Thus, a pellet of a flame-retardant polyester resin composition was obtained. When obtaining the said polyester pellet, the bad smell was bad and the malfunction that smoke generate | occur | produced generate | occur | produced. It is thought that the cause was that there were many volatile components by the low molecular weight of flame retardant A2. Let this polyester be a recovery flame-retardant polyester-based resin composition (6). Table 1 shows the intrinsic viscosity of the recovered flame-retardant polyester resin composition (6) and the phosphorus element content obtained by ICP.

  Polyester raw material (3), polyester raw material (6), recovered flame retardant polyester resin composition (6) mixed in a ratio of 2.5: 54.5: 43.0 as a raw material, and a diameter of 90 mm Using a twin-screw extruder with a vent, the discharge rate: 450 kg / hr, cylinder temperature: 290 ° C., melt-extruded, and the amorphous polyester sheet flowing out from the die was brought to a surface temperature of 40 ° C. using an electrostatic application adhesion method. It was rapidly cooled and solidified on the set casting drum to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  In addition, when forming the polyester film using the said polyester, there was a problem that a bad odor was bad and smoke was generated. In addition, breakage occurred frequently during film formation, and the yield was low.

Comparative Example 1:
Using the polyester raw material (2), the polyester raw material (3), and the polyester (5) mixed at a ratio of 92.5: 2.5: 5.0 as a raw material, using a twin screw extruder with a vent of 90 mm in diameter , Discharge amount: 450 kg / hr, cylinder temperature: melt-extruded at 290 ° C., the amorphous polyester sheet flowing out from the die was rapidly cooled on a casting drum set to a surface temperature of 40 ° C. using an electrostatic application adhesion method Solidified to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer.

  The obtained pulverized product is dried and then supplied to a single screw extruder. After the melt extrusion in a 290 ° C. environment, the pelletized polyester is used as a recovered flame-retardant polyester resin composition (7). The intrinsic viscosity (dl / g) of the obtained polyester was 0.65. Table 1 shows the intrinsic viscosity of the recovered flame-retardant polyester resin composition (7) and the phosphorus element content obtained by ICP.

  Polyester raw material (2), polyester raw material (3), polyester (5), and recovered flame-retardant polyester-based resin composition (7) in a ratio of 74.0: 2.0: 4.0: 20.0 The mixed polyester is used as a raw material and melted and extruded at a discharge rate of 450 kg / hr and a cylinder temperature of 290 ° C. with a vented twin screw extruder having a diameter of 90 mm. Was used to quench and solidify on a casting drum whose surface temperature was set to 40 ° C. to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a polyester film master roll having a thickness of 50 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut-separated ear film and slit ear were pulverized by a pulverizer and stored for recovered polyester.

Comparative Example 2:
The polyester raw material (2), the polyester raw material (3), and the polyester (5) mixed at a ratio of 76.5: 2.0: 21.0 are used as a raw material, and a biaxial extruder with a vent having a diameter of 90 mm is used. , Discharge amount: 450 kg / hr, cylinder temperature: melt-extruded at 290 ° C., the amorphous polyester sheet flowing out from the die was rapidly cooled on a casting drum set to a surface temperature of 40 ° C. using an electrostatic application adhesion method Solidified to obtain an unstretched single layer sheet. Next, the film was stretched 3.2 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then led to a tenter, and the longitudinally stretched sheet held by a clip was stretched 3.8 times in the transverse direction at 120 ° C. Then, after heat treatment at 210 ° C., it was relaxed to obtain a master roll of a polyester film having a thickness of 150 μm and a width of 2000 mm. When the master roll was obtained, it became thick due to the neck-in phenomenon from the base, and the end portion of the polyester film used as a clip bite was cut and separated as an ear film. A slit was made from a position 400 mm from both ends of the master roll to obtain a polyester film having a product width of 1200 mm. Table 1 shows the film formability and flame retardancy of the polyester film.

  At the time of this slit, the generated surplus was cut and separated as a slit ear. The cut ear film and slit ear were discarded. Since the polyester does not contain any recovered flame retardant polyester resin composition and discards surplus, it is not preferable from the viewpoint of environmental load and cost.

  The resin composition of the present invention can be suitably used, for example, in various applications where flame retardancy is required.

1 Clamp 2 Tape 3 125mm Mark 4 Burner 5 Cotton

Claims (4)

A flame-retardant polyester-based resin composition containing a recovered polyester component and containing 0.20% by weight or more of a phosphorus element. The flame-retardant polyester-based resin composition according to claim 1, comprising a phosphorus-containing compound represented by the following formula (1).

The flame-retardant polyester resin composition according to claim 1 or 2, having an intrinsic viscosity of 0.45 dl / g or more. A flame-retardant polyester film containing the flame-retardant polyester resin composition according to claim 1.

Images