WO2001053377A1 - Film polyester ininflammable - Google Patents

Film polyester ininflammable Download PDF

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Publication number
WO2001053377A1
WO2001053377A1 PCT/JP2001/000292 JP0100292W WO0153377A1 WO 2001053377 A1 WO2001053377 A1 WO 2001053377A1 JP 0100292 W JP0100292 W JP 0100292W WO 0153377 A1 WO0153377 A1 WO 0153377A1
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WO
WIPO (PCT)
Prior art keywords
film
polyester
flame
phosphorus
polyester film
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Application number
PCT/JP2001/000292
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English (en)
Japanese (ja)
Inventor
Minako Shimizu
Katsuya Ito
Naonobu Oda
Hideo Takeuchi
Katufumi Kumano
Shinsuke Yamaguchi
Original Assignee
Toyo Boseki Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Priority to JP2001553843A priority Critical patent/JP3575605B2/ja
Publication of WO2001053377A1 publication Critical patent/WO2001053377A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus

Definitions

  • the present invention relates to a transparent, translucent, and opaque flame-retardant polyester film.
  • packaging materials membrane switches, sunset panels, projector screens, labels, building materials such as wallpaper and steel sheet lamination, recording paper for printers such as ink receiving paper, various process papers such as fuel cells, adhesives Transparent polyester film with excellent flame retardancy, translucent polyester film, opaque, used for coating materials such as tapes and electronic components, flat cables, interlayer insulators for molded coils of molded transformers, printed wiring boards, etc. It relates to polyester films. Background art
  • Polyester has excellent physical and chemical properties, and is superior to other synthetic resins in terms of handleability and price.Therefore, polyester is widely used in a wide variety of fields such as fibers, films, and molded products. I have. Textiles are used for clothing, bedding, curtains, carpets, etc.Films are used for magnetic tapes, capacitors, and photographic base films, and molded products are used for daily life such as home appliances and electronic machinery. ing.
  • polyester is generally flammable, and attempts have been made to impart flame retardancy to various polyester processed products from the viewpoint of fire prevention.
  • Methods for imparting flame retardancy to polyester include a post-processing method in which a flame retardant is applied in the final step of a product, a method in which a flame retardant is added to a polymer, and a method in which a flame retardant is copolymerized into a polymer.
  • polyester films having various functions have become active.
  • the void-containing polyester film contains a thermoplastic resin such as polyolefin-polystyrene, which is incompatible with polyester, as a void developing agent, and contains a lot of air in the void. There is a problem of poor flame retardancy.
  • Japanese Patent Publication No. 49-22958 discloses a method of copolymerizing a phosphate ester with a polyester as a phosphorus compound
  • Japanese Patent Application Laid-Open No. 59-91122 discloses a phosphone compound as a phosphorus compound.
  • the method of copolymerizing an acid contains a phosphorus compound having a special ester-forming functional group in JP-B-36-20771 and JP-A-52-142796.
  • Japanese Patent Publication No. Sho 533-134979 discloses a method of copolymerizing carboxyphosphinic acid
  • Japanese Patent Application Laid-Open No. 140521/1991 discloses a method of copolymerizing a phosphoxide derivative. Have been.
  • copolymers of polyester with phosphate esters have the disadvantage that the molecular weight is reduced during molding. This is introduced into the polyester backbone This is presumably because the P-0 bond is weak, and the polyester main chain is cleaved at this portion, thereby lowering the hydrolysis resistance of the polyester.
  • Japanese Patent Application Laid-Open No. 48-55950 discloses a flame-retardant polyester composition comprising a compound containing a halogen and phosphorus in the molecule.
  • JP-A-48-91313, JP-A-49-110242, JP-A-59-59916 discloses a method of using a composition prepared by blending a phosphorus compound as a film. Halogen was not included, and flame retardancy, heat resistance, hydrolysis resistance, and bleed-out resistance were not fully satisfied.
  • Japanese Patent Application Laid-Open No. 9-111100 proposes a phosphorus compound having good bleed-out resistance.
  • a phosphorus compound having good bleed-out resistance.
  • a copolymer a copolymer that is compared with a copolymer.
  • the amount of phosphorus compound precipitated in the melt extrusion process during film production increases, and the operability deteriorates due to an increase in the filtration pressure of the filter during long-term operation.
  • Japanese Patent Application Laid-Open No. 6-79946 discloses a method of laminating a layer containing a large amount of a flame-retardant element on both sides of a layer containing a small amount of a flame-retardant element.
  • a small amount of the flame retardant element layer is present, the amount of the flame retardant element in the entire film is reduced, and the flame retardancy of the entire film is reduced.
  • the amount of flame-retardant elements on the film surface is increased in order to improve the flame retardancy, the heat resistance of the film surface will be reduced, causing a practical problem.
  • a first invention of the present invention is a copolymerized polyester film containing a phosphorus compound represented by the following general formula (1), wherein the phosphorus compound with respect to polyester is 1,500 to 5, It is a flame-retardant polyester film characterized by containing 0.000 O ppm.
  • R i is a monovalent ester-forming functional group
  • R 2 and R 3 are the same or different groups, and each is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, Selected from R i
  • A represents a divalent or trivalent organic residue
  • ni represents 1 or 2
  • n 2 and n 3 each represent an integer of 0 to 4.
  • a second invention is the flame retardant according to the first invention, wherein the film has a heat shrinkage at 150 ° C. of at least one of 3% or less in a vertical or horizontal direction. It is a crystalline polyester film.
  • a third invention is the flame-retardant polyester film according to the first or second invention, wherein the film contains a divalent metal compound in an amount of 1 to 150 ppm as a divalent metal with respect to polyester. It is.
  • a fourth invention is the flame-retardant polyester according to the third invention, wherein the divalent metal is zinc.
  • a fifth invention is the flame-retardant polyester film according to any one of the first, second, third, and fourth inventions, wherein the light transmittance of the film is 80% or more. is there.
  • a sixth invention is the flame-retardant polyester film according to any one of the first, second, third and fourth inventions, wherein the light transmittance of the film is less than 80%. .
  • a seventh invention is the flame-retardant polyester according to any one of the first, second, third, fourth, fifth and sixth inventions, wherein the film contains inorganic particles and / or organic particles. Film.
  • Eighth aspect of the film contains a large number of fine voids inside thereof, an apparent density of 0.5 to 1 of the film.
  • S g Z first, characterized in that cm is 3, 2, 3,
  • embodiments of the flame-retardant polyester film of the present invention will be described in detail.
  • the polyester in the present invention is composed of an acid component and a diol component.o
  • Acid components include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, bis (4-carboxyphenyl) ether, bis ( Aromatic dicarboxylic acids such as 4-carboxyphenyl) sulfone, 1,2-bis (4-carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid, 2.5-dibromoterephthalic acid, and tetrabromoterephthalic acid And aliphatic dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; and lower alcohol esters thereof. Also, oxycarboxylic acid or its ester-forming derivative can be used as the total acid component.
  • the diol component includes ethylene glycol, propylene glycol, ethylene glycol, neopentyl glycol, 1.2_propylene glycol, 1 1,4-butanediol, 1.6-hexanediol, 1,4-cyclohexanedimethanol, 1,1-decamethylene glycol, 4.4 dihydroxybisphenol, 1,4-bis (/ 3-Hyd ⁇ -xyethoxy) benzene, 2,5-naphthylene diol, glycol obtained by adding ethylene oxide to these glycols, polyethylene glycol, bisphenol A, bisphenol S, and the like.
  • the terminal of the 0 H group of the polyester can be blocked.
  • thermal decomposition of polyester is suppressed, thermal stability is improved, and the amount of generated gas is further reduced.
  • polymerization method and the polymerization catalyst for example, those conventionally used in the production of polyester, such as a known method described in Japanese Patent Publication No. 55-41610, can be used without any particular limitation. .
  • an antimony compound as a catalyst, since the color tone is improved by including a specific amount of a divalent metal.
  • antimony catalyst examples include antimony compounds such as antimony trioxide, antimony pentoxide, antimony glycolate, antimony glycolate, antimony acetate, and antimony phenolate.
  • the main raw material polymer used in the flame-retardant polyester film of the present invention is a polyester obtained by copolymerizing the phosphorus compound represented by the general formula (1).
  • Phosphorus compounds are compounds that can react with polyester didiol sulfonic acid, which is a constituent component of polyester, to be copolymerized with polyester.
  • the phosphorus compound is preferably a compound capable of introducing a phosphorus atom into the side chain and / or the terminal of the polyester, and particularly preferably a compound capable of introducing a phosphorus atom into the side chain.
  • Examples of the compound represented by the general formula (1) include compounds represented by the following (a) to () 3). [Formula 2]
  • the phosphorus compound is an organic phosphorus compound represented by the following general formula (2) and represented by '6-oxo-1 (6H) -dibenzo- (c, e) (1,2) -oxaphospholine (DOP).
  • DOP '6-oxo-1
  • c, e dibenzo-
  • DOP -oxaphospholine
  • a DOP derivative in which an organic group is introduced is preferable.
  • R 1 , R 2 , m, and n are the same as described above.
  • A represents the same or different organic group as R 1 and R 2.
  • DOP is a reaction of an orthofluorophenolic compound (hereinafter, also referred to as ⁇ PP) with a phosphorus compound such as phosphorus trihalide (PX 3 : X represents a halogen atom), and furthermore, zinc chloride or the like. It can be produced by, for example, a method of condensing under heating in the presence of a divalent metal compound of a Friedel-Crafts type catalyst, followed by hydrolysis with water under heating.
  • the divalent metal compound used as the catalyst remains in the DOP.
  • a large amount of a divalent metal compound is present in the DOP derivative copolymerized with the polyester, an insoluble substance is easily formed by forming a complex with an antimony compound which is a general polymerization catalyst of the polyester.
  • the color tone also decreases.
  • the antimony compound is reduced and the polyester is darkened. That is, by adding a divalent metal compound to such an extent that a complex is not formed in the DOP, the phosphorus copolymer polyester having a good color tone can be obtained.
  • the color tone of the polyester becomes good.
  • the amount of the divalent metal is less than 1 ppm with respect to the polyester, the amount of The reduction of the mon compound is not sufficiently suppressed, and the color tone of the polyester is not improved.
  • the amount of the divalent metal exceeds 50 ppm, the thermal stability deteriorates, so that the polymer is colored due to the heat history in the melt extrusion step or the like during film production, and the color tone of the film is impaired.
  • the amount of the valent metal is preferably 5 Oppm or less, and more preferably 30 ppm or less.
  • zinc is particularly preferred for improving the color tone of the polyester.
  • Examples of a method for allowing the polyester to contain the divalent metal compound include a method in which an appropriate amount of the divalent metal compound is left in the DOP production process, a method in which the DOP derivative is produced, or a method in which the divalent metal compound is added during polyester polymerization.
  • the present invention is not limited to these methods. Further, several kinds of divalent metal compounds may be contained.
  • the above phosphorus compound it is necessary for the above phosphorus compound to contain 1,500 to 50,000 ppm as a phosphorus atom to the polyester from the viewpoint of flame retardancy and heat resistance.
  • the content of phosphorus atoms in the polyester is preferably at least 2,000 ppm, more preferably at least 3,000 ppm.
  • the content of phosphorus atoms is preferably 20. OOOppm or less, more preferably 15. OOOppm or less.
  • the copolymer polyester used as a raw material of the flame-retardant polyester film of the present invention can be polymerized by a known method, for example, as described in JP-B-55-41610.
  • the copolymerized polyester preferably has an intrinsic viscosity of 0.50 to 0.80 dlZg. Particularly preferably, it is 0.55 to 0.70 dlZg. If the intrinsic viscosity is less than 0.50 d1 ng, breakage is likely to occur during film production. On the other hand, if it exceeds 0.80 dlZg, the heat shrinkage of the film at 150 at the time of forming a film becomes worse and the film becomes harder, and the discharge pressure at the time of extruding the molten resin increases, so that stable extrusion tends to be difficult. . Other flame retardants can be added as needed to further improve the flame retardancy.
  • the present invention is used not only for applications where the light transmittance of the film is required to be 80% or more, but also for applications where the light transmittance is less than 80% and the need for translucency or opacity is required. be able to.
  • the light transmittance of the film is preferably less than 80%, more preferably less than 60%, and still more preferably less than 40%. It is particularly preferably less than 20%.
  • the light transmittance of the film is 80% or more, the transparency is too high, and the print clarity when printed tends to be poor.
  • the copolymerized polyester contains inorganic particles and / or organic particles.
  • the particles can be mixed with a copolyester, melted and extruded, and then stretched in at least one axial direction, so that voids can be developed around the particles.
  • the inorganic particles are not particularly limited, but include, for example, silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, zinc sulfide, and the like.
  • the organic particles are not particularly limited, but examples thereof include heat-resistant polymer particles such as cross-linked polystyrene, cross-linked acrylic particles, and benzoguanamine particles.
  • titanium oxide and zinc sulfide are preferred in terms of concealing properties. Further, titanium oxide is most preferable because the film can effectively impart hiding power and a clear image is easily obtained. Titanium oxide may be any of anatase type and rutile type. Further, the surface of the titanium oxide may be subjected to an inorganic surface treatment such as alumina or silica, or may be subjected to an organic surface treatment such as a silicon-based or alcohol-based surface treatment. Calcium carbonate and barium sulfate are preferred because the color b value (a measure of yellow tint) of the film is easily lowered and the color tone is improved.
  • a film containing cavities having fine bubbles inside the film is also suitable for reducing the light transmittance to less than 80%.
  • the method of containing a cavity therein include a method of mixing a foaming agent with a resin, and the like.
  • a copolymerized polyester is used.
  • Incompatible thermoplastic resins include polystyrene resin and polyolefin resin.
  • void containing polyester film is preferably an apparent density of 0. 5 ⁇ 1. 3g "cm 3, more preferably 0. 7 ⁇ 1. SgZcm 3, particularly good Mashiku 0.8 to 1. 2g / cm 3. Inclusion of voids inside provides good cushioning, drawing properties, and good workability in building materials, etc. If the apparent density of the film is 0. SgZcm 3 or less, the waist is weak. become a film, the lack of drawing of Ya cushioning in 1. 3gZ cm 3 or more.
  • the flame-retardant polyester film of the present invention may contain additives other than those described above.
  • additives include pigments such as carbon black, ultraviolet absorbers, fluorescent brighteners, antioxidants, antistatic agents, antiglare agents, and the like.
  • the copolymerized polyester is vacuum-dried with a drier, preferably vacuum-dried to a water content of 50 ppm or less, and used as a film raw material.
  • the unstretched sheet is manufactured by a known film forming method such as a cast-in-glass method or a force render method.
  • the polyester preferably has a melting specific resistance of 0.1 to 10 ( ⁇ 10 8 ⁇ ⁇ ⁇ ), and particularly preferably 0.1 to 5 (X 10 8 ⁇ ⁇ cm).
  • the content of the phosphorus compound in the formed polyester is set to 1,500 to 20, OOOppm in terms of phosphorus atom.
  • a phosphorus atom is introduced into the polyester side chain.
  • Particularly preferred are phosphorus compounds which can be incorporated.
  • the unstretched sheet is heated at a temperature in the range of 3 ° C. or more higher than the glass transition temperature (T g) to less than the crystallization onset temperature (T el), preferably (T g + 5 ° C.)
  • T g glass transition temperature
  • T el crystallization onset temperature
  • the film is uniaxially stretched 1.5 to 4.8 times in the longitudinal or width direction of the film. If necessary, in the direction perpendicular to the stretching direction, at a temperature of (Tg + 3 ° C) to (Tc1-5 ° C), preferably (Tg + 5 ° C) to (Tc1— At a temperature of 5 ° C), stretch by 1.5 to 4.8 times.
  • the stretching of the film can be performed by a method such as simultaneous biaxial stretching, sequential biaxial stretching, or uniaxial stretching, and the stretching of the film may be performed in either the longitudinal direction or the width direction first. Further, it is preferable to perform heat setting at 180 to 240 ° C. for 1 to 60 seconds. Performing such a heat-setting treatment is suitable for setting the heat shrinkage in the longitudinal and transverse directions at 150 ° C. in the range of ⁇ 0.1 to 3.0%. In addition, during the heat setting process and / or after the heat setting process, 1% to 10% relaxation in the horizontal and / or vertical direction may be used together, and the heat shrinkage in the vertical and horizontal directions at 150 ° C may be used. It is effective in reducing the rate.
  • the flame-retardant polyester film of the present invention preferably has a heat shrinkage of 3% or less at 150 ° C. in at least one of the vertical and horizontal directions. It is particularly preferably at most 2%. If the heat shrinkage exceeds 3%, sealing force tends to occur due to heat treatment in the post-processing step.
  • the film of the present invention can have another polymer layer laminated on the surface.
  • the method for forming the polymer layer is not particularly limited. Examples thereof include a method of co-extruding and laminating another polymer simultaneously with the phosphorus compound copolymerized polyester of the present invention at the time of film formation, and a method of forming another film on the phosphorus-containing polyester film. There are a method of coating and laminating a polymer coating layer, and a method of bonding a polymer film with an adhesive or the like.
  • a coating layer containing a polymer resin as a main component on the film surface by providing a coating layer containing a polymer resin as a main component on the film surface, the wettability and adhesion of inks and coating agents are improved.
  • a polymer resin a polyester resin is preferable.
  • other ordinary polyethers such as polyurethane resin, polyester urethane resin and acrylic resin
  • a polymer resin that improves the adhesiveness of the stell film can be used.
  • a method of applying the coating solution to the film As a method of applying the coating solution to the film, a method of applying the coating solution to an unstretched sheet and stretching the film at least in a uniaxial direction, and a method of applying the coating solution to a surface of a cavity-containing film stretched in a uniaxial direction.
  • any method such as a method in which the film is stretched in the perpendicular direction thereof, a method in which the film is applied to the surface of the polyester film which has been subjected to the stretching treatment, and the like can be used.
  • Apparatuses for applying the coating liquid include gravure coating, kiss coating, dip coating, spray coating, curtain coating, air knife coating, blade coating, and reverse roll coating.
  • the device can be applied.
  • these flame-retardant polyester films can be subjected to various types of processing to impart desired performance.
  • irradiation with ultraviolet rays, rays, r rays,) three rays or electron beams, surface activation treatments such as corona treatment, plasma treatment, and flame treatment may be mentioned.
  • These surface activation treatments can increase the wet tension of the film surface (45 to 70 dyne'cm) and are suitable for use in post-processing such as printing. Also, good printability can be obtained even when an easily adhesive resin coating solution is applied to the film surface and dried.
  • the moisture permeability is 1 to 70 g / m 2 '24 hr and the oxygen permeability is 0.1 to 150 cc / m 2 '24 hr.
  • a resin such as polyvinylidene chloride, polyvinyl alcohol, polyamide, or polyolefin is applied to the film surface and laminated, or aluminum oxide, silicon oxide, or a composite oxide thereof is deposited. Is preferred.
  • the flame-retardant polyester film of the present invention preferably has a thickness of 5 to 500 m. If the thickness of the film is less than 5 m, breakage tends to occur during film formation, and stable operation tends to be difficult. On the other hand, if the thickness of the film exceeds 500 ⁇ m, the impact resistance tends to decrease. More preferably, it is 10 to 300 m.
  • the resulting flame-retardant polyester film is an indicator of flame retardancy, UL 94- The flame retardancy rank measured according to the VTM standard is preferably VTM-2 or higher.
  • the total light transmittance (%) was determined with NDH-1001 DP manufactured by Nippon Denshoku Industries Co., Ltd.
  • the film was cut into four squares of 5.00 cm square to make a sample. Four of these are stacked, and the thickness is measured with a micrometer at 10 places with 4 significant figures.
  • the average value of the thickness of the four sheets was determined. The average value was divided by 4 and rounded to three significant figures to obtain the average film thickness per sheet (t: ⁇ ).
  • the weight (w: g) of the four samples was measured using an automatic precision balance with 4 significant figures, the apparent density was determined by the following formula, and rounded to 3 significant figures. The smaller the apparent density, the better the flexibility and cushioning.
  • the polyester film was measured with a color chromaticity meter (CR-220 manufactured by Minolta) on a color tone measurement reference plate.
  • a color chromaticity meter (CR-220 manufactured by Minolta) on a color tone measurement reference plate. The larger the value of L *, the higher the brightness, and the larger the absolute value of both a * and b *, the more the color is colored.
  • Production Example 1-1 a hydrolysis reaction was carried out in the same manner as in Example 1-1, except that purification with toluene was not performed after the production of DO PX. Thereafter, the product was cooled by adding 1000 parts of toluene. Next, the product was cooled and a solid product was filtered out and washed with 300 parts of toluene to obtain a powdery DOP composition. Table 1 shows the zinc metal content, chlorine atom content, and impurity organic compound content of the DOP composition. Production example 1 1 3
  • Production Example 2-1 in place of the DOP obtained in Production Example 1-1, Production Example 1 A compound corresponding to compound (s) was produced in the same manner as in Production Example 2-1 except that D ⁇ P obtained in —2 was used. An insoluble complex was observed in the obtained compound.
  • Production Example 2-3 In Production Example 2-1, in place of the DOP obtained in Production Example 1-1, Production Example 1 A compound corresponding to compound (s) was produced in the same manner as in Production Example 2-1 except that D ⁇ P obtained in —2 was used. An insoluble complex was observed in the obtained compound. Production Example 2-3
  • Production Example 2-1 the compound (s) was prepared in the same manner as in Production Example 2-1 except that the DOP obtained in Production Example 1-3 was used instead of the DOP obtained in Production Example 1-1. A compound corresponding to was prepared. No insoluble complex was found in the obtained compound.
  • Production Example 3-1 Synthesis of polyester
  • Production Example 3-1 was prepared in the same manner as in Production Example 3-1 except that the DOP derivative composition obtained in Production Example 2-2 was used instead of the DOP derivative composition obtained in Production Example 2-1. Similarly, a copolymerized polyester was produced. Table 2 shows the zinc metal content, the phosphorus content and the intrinsic viscosity in the obtained copolyester. Production example 3-4
  • Preparation Example 3-2 the same as Preparation Example 3-2 except that the DOP derivative composition obtained in Preparation Example 2-3 was used instead of the DOP derivative composition obtained in Preparation Example 2-1 Thus, a copolymerized polyester was produced.
  • Table 2 shows the zinc metal content, the phosphorus content and the intrinsic viscosity in the obtained copolyester.
  • Production example 3-5 the same as Preparation Example 3-2 except that the DOP derivative composition obtained in Preparation Example 2-3 was used instead of the DOP derivative composition obtained in Preparation Example 2-1 Thus, a copolymerized polyester was produced. Table 2 shows the zinc metal content, the phosphorus content and the intrinsic viscosity in the obtained copolyester.
  • Preparation Example 3-1 the DOP derivative composition obtained in Preparation Example 2-3 was used in place of the DOF derivative composition obtained in Preparation Example 2-1.
  • a copolymerized polyester was produced in the same manner as in Production Example 3-1 except that 0.84 part ( ⁇ ⁇ mZ polyester) of an ethylene glycol solution of zinc acetate in toluene was added.
  • Table 2 shows the zinc metal content, the phosphorus content, and the intrinsic viscosity in the obtained copolymerized polyester.
  • a polyester was produced in the same manner as in Production Example 3-1 except that the DOP derivative composition obtained in Production Example 2-1 was not added.
  • Table 2 shows the zinc metal content, phosphorus content and intrinsic viscosity in the obtained polyester. Manufacturing example 3-7
  • Production Example 3 was the same as in Production Example 3-1, except that 437 parts of terephthalic acid and 11 parts of the DO p derivative composition obtained in Production Example 2-1 (phosphorus content to polyester obtained: 1000 ppm) were used. — Produce copolyester in the same manner as in 1. did. Table 2 shows the zinc metal content, phosphorus content, and intrinsic viscosity in the obtained polyester. Production Example 3-8
  • Preparation Example 3-1 16 parts of terephthalic acid, and 6-16 parts of the D ⁇ F derivative composition obtained in Preparation Example 2-1 (phosphorus content of 500,000 ppm based on polyester obtained) Before esterification, copolymerization was carried out in the same manner as in Production Example 3-1 except that 20 g Z liter of 0.84 parts of a zinc acetate ethylene glycol solution (10 ppm m polyester) was added. Polyester was produced. Table 2 shows the zinc metal content, the phosphorus content and the intrinsic viscosity in the obtained copolymerized polyester. Manufacturing Example 3-9
  • Production Example 3-1 instead of the DOP derivative composition obtained in Production Example 2-1, an ethylene glycol ester of methylphosphinic acid was charged so that the amount of phosphorus element was 1000 ppm with respect to polyester. Other than that, a polyester was produced in the same manner as in Production Example 3_1. Production example 3—10
  • the phosphorus-containing copolymerized polyester resin produced in Production Example 3-1 was vacuum-dried at 175 ° C for 2 hours using a rotary vacuum dryer having a steam jacket, and then a molding temperature of 260 ° C and a press pressure of 29.4 MPa. The melt was pressed under the condition of a molding time of 1 minute to obtain an unstretched sheet having a thickness of 350 im. This unstretched sheet is simultaneously biaxially stretched 3.5 times in the machine and width directions at 90 ° C, and then heat-set at 230 ° C for 15 seconds to obtain a 25 ⁇ m thick polyester film. I got Table 3 shows the properties of the obtained film.
  • Example 3 A polyester film was obtained in the same manner as in Example 1, except that the phosphorus-containing copolymerized polyester produced in Production Example 3-2 was used. Table 3 shows the properties of the obtained film. Example 3
  • Example 4 A polyester film was obtained in the same manner as in Example 1 except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was used. Table 3 shows the properties of the obtained film.
  • Example 4 A polyester film was obtained in the same manner as in Example 1 except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was used. Table 3 shows the properties of the obtained film.
  • Example 4 A polyester film was obtained in the same manner as in Example 1 except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was used. Table 3 shows the properties of the obtained film. Example 4
  • the phosphorus-containing copolymerized polyester resin produced in Production Example 3-1 was vacuum-dried at 175 ° C for 2 hours using a rotary vacuum dryer having a steam jacket, and then pressed at a molding temperature of 260 ° C. Melt pressing was performed under the conditions of a pressure of 29.4 MPa and a molding time of 1 minute to obtain an unstretched sheet having a thickness of 1550 m. This unstretched sheet was simultaneously biaxially stretched 3.5 times in the longitudinal and width directions at 90 ° C, and then heat-set at 230 ° C for 15 seconds to obtain a sheet having a thickness of 125 m. A polyester film was obtained. Table 3 shows the properties of the obtained film.
  • Example 5 shows the properties of the obtained film.
  • Example 6 A polyester film was obtained in the same manner as in Example 4 except that the phosphorus-containing copolymerized polyester produced in Production Example 3-2 was used. Table 3 shows the properties of the obtained film.
  • Example 6 A polyester film was obtained in the same manner as in Example 4 except that the phosphorus-containing copolymerized polyester produced in Production Example 3-2 was used. Table 3 shows the properties of the obtained film.
  • Example 6 A polyester film was obtained in the same manner as in Example 4 except that the phosphorus-containing copolymerized polyester produced in Production Example 3-2 was used. Table 3 shows the properties of the obtained film. Example 6
  • Example 7 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was used. Table 3 shows the properties of the obtained film.
  • Example 7 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was used. Table 3 shows the properties of the obtained film.
  • Example 7 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was used. Table 3 shows the properties of the obtained film. Example 7
  • Example 8 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Example 3-3 was used. Table 3 shows the properties of the obtained film.
  • Example 8 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Example 3-3 was used. Table 3 shows the properties of the obtained film.
  • Example 8 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Example 3-3 was used. Table 3 shows the properties of the obtained film.
  • Example 8 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Example 3-3 was used. Table 3 shows the properties of the obtained film.
  • Example 8 A polyester film was obtained in the same manner as in Example 4, except that the phosphorus-containing copolymerized polyester produced in Production Example 3-3 was used. Table 3 shows the properties of the obtained film.
  • Example 8 A polyester
  • Example 9 A polyester film was obtained in the same manner as in Example 5, except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-4 was used. Table 3 shows the properties of the obtained film. However, in the obtained film, a defect that was considered to be derived from an insoluble material was observed. Example 9
  • Example 3-2 Using a rotary vacuum dryer with a steam jacket, vacuum-dried at 175 ° C for 2 hours for 2 hours.
  • Preparation of phosphorus-containing copolymerized polyester resin 98.5% by weight in Example 3-2 and silica 1.5 wt% of particles (Silicia 430, manufactured by Fuji Silicia) are melt-mixed with a twin-screw extruder, extruded from a T-die into a rotating cooling metal roll in a sheet form, and pressed while electrostatically adhering. A stretched sheet was obtained.
  • Example 10 After stretching this unstretched sheet 3.3 times at 90 in the longitudinal direction with rolls with different speeds, it is stretched 3.7 times at 125 ° C in the transverse direction with a tenter, Subsequently, a polyester film having a thickness of 75 m was obtained by heat-setting at 230 ° C. while relaxing 4% in the horizontal direction. Table 4 shows the properties of the obtained film.
  • Example 10 After stretching this unstretched sheet 3.3 times at 90 in the longitudinal direction with rolls with different speeds, it is stretched 3.7 times at 125 ° C in the transverse direction with a tenter, Subsequently, a polyester film having a thickness of 75 m was obtained by heat-setting at 230 ° C. while relaxing 4% in the horizontal direction. Table 4 shows the properties of the obtained film.
  • Example 10 After stretching this unstretched sheet 3.3 times at 90 in the longitudinal direction with rolls with different speeds, it is stretched 3.7 times at 125 ° C in the transverse direction with a tenter, Subsequently,
  • Example 1 1 Same as Example 9 except that the phosphorus-containing copolymerized polyester resin produced in Production Example 3-1 was 97% by weight, the silica particles were 3% by weight, and the final film thickness was 100 m. To obtain a polyester film. Table 4 shows the properties of the obtained film.
  • Example 1 1 the phosphorus-containing copolymerized polyester resin produced in Production Example 3-1 was 97% by weight, the silica particles were 3% by weight, and the final film thickness was 100 m.
  • Table 4 shows the properties of the obtained film.
  • Example 9 the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was replaced with 9 A polyester film was obtained in the same manner as in Example 9 except that 3% by weight, silica particles were 7% by weight, and the final film thickness was 100 m. Table 4 shows the properties of the obtained film.
  • Example 12 the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was replaced with 9 A polyester film was obtained in the same manner as in Example 9 except that 3% by weight, silica particles were 7% by weight, and the final film thickness was 100 m. Table 4 shows the properties of the obtained film.
  • Example 12 the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was replaced with 9 A polyester film was obtained in the same manner as in Example 9 except that 3% by weight, silica particles were 7% by weight, and the final film thickness was 100 m. Table 4 shows the properties of the obtained film.
  • Example 12 the phosphorus-containing copolymerized polyester produced in Production Examples 3-5 was replaced with 9 A polyester
  • Example 9 90% by weight of the phosphorus-containing copolymerized polyester produced in Production Example 3-2 and 10% by weight of anatase-type titanium dioxide (TA-300, manufactured by Fuji Titanium Co.) were used. A polyester film was obtained in the same manner as in Example 7, except that 125 was used. Table 4 shows the properties of the obtained film.
  • Example 13 90% by weight of the phosphorus-containing copolymerized polyester produced in Production Example 3-2 and 10% by weight of anatase-type titanium dioxide (TA-300, manufactured by Fuji Titanium Co.) were used. A polyester film was obtained in the same manner as in Example 7, except that 125 was used. Table 4 shows the properties of the obtained film.
  • Example 13 90% by weight of the phosphorus-containing copolymerized polyester produced in Production Example 3-2 and 10% by weight of anatase-type titanium dioxide (TA-300, manufactured by Fuji Titanium Co.) were used. A polyester film was obtained in the same manner as in Example 7, except that 125 was used. Table 4 shows the properties of the obtained
  • This unstretched sheet was stretched 3.3 times in the longitudinal direction at 90 ° C with rolls having different speeds, and then stretched 3.7 times in the transverse direction at 125 ° C with a tenter.
  • a flame-retardant void-containing polyester film with a thickness of 75 m was obtained. Table 5 shows the properties of the obtained film.
  • Example 11 88% by weight of the phosphorus-containing copolymerized polyester produced in Production Example 3-1, 7.5% by weight of a polypropylene resin (F102WC, manufactured by Grand Polymer Co., Ltd.), anatase-type titanium dioxide (Fuji Titanium) Co., Ltd., TA-300) was 2% by weight, and the final film thickness was 125 ⁇ m. Table 5 shows the properties of the obtained film. Comparative Example 1
  • a polyester film was obtained in the same manner as in Example 1, except that the polyester produced in Production Examples 3-6 was used. Table 3 shows the properties of the obtained film. Comparative Example 2
  • a polyester film was obtained in the same manner as in Example 4, except that the polyester produced in Production Examples 3-6 was used. Table 3 shows the properties of the obtained film. Comparative Example 3
  • a polyester film was obtained in the same manner as in Example 6, except that the polyester produced in Production Examples 3-6 was used. Table 3 shows the properties of the obtained film. Comparative Example 4
  • a polyester film was obtained in the same manner as in Example 10 except that the phosphorus-containing copolymerized polyester produced in Production Examples 3-7 was used. Table 4 shows the properties of the obtained film. Comparative Example 9
  • a polyester film was obtained in the same manner as in Example 13 except that the polyester produced in Production Examples 3-6 was used. Table 5 shows the properties of the obtained film.
  • the flame-retardant polyester film of the present invention can be achieved by the conventional method because a specific amount of a novel flame-retardant containing a phosphorus atom is co-polymerized in the polyester main chain during the production of the polyester resin as a raw material for the film. Has no flame retardancy. Further, the same excellent flame retardancy can be obtained for a translucent or opaque void-containing polyester film which is disadvantageous in terms of flame retardancy as compared with a normal polyester film. Furthermore, by including a divalent metal compound in the polyester as a divalent metal, preferably a specific amount of zinc, a polyester film having a good color tone can be obtained even when an antimony-based catalyst is used.
  • packaging materials membrane switches, touch panels, projector screens, labels, building materials such as wallpaper and steel sheet lamination, recording paper for printers such as ink-receiving paper, various process papers such as fuel cells, adhesive tape, and electronics It is suitable for a wide range of applications, such as coating materials for parts, flat cables, long insulation for molded transformers in molded transformers, and printed wiring boards.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un film polyester ininflammable composé d'un film de copolyester renfermant un composé phosphore de la formule générale (1), dans laquelle la teneur en composé phosphore est comprise entre 1500 et 50000 mg/l du polyester en termes de quantité d'atomes de phosphore. Le film de l'invention possède des propriétés ignifugeantes jamais atteintes dans l'état antérieure de la technique. Dans la formule (1), R1 est un groupe fonctionnel monovalent formateur d'ester ; R2 et R3 sont les mêmes ou différents et chacun représente un élément choisi parmi des groupes halogéno, hydrocarbures en C1-10 et le même groupe que R1 ; A représente un résidu organique di- ou trivalent ; n1 est égal à 1 ou 2 ; et n2 et n3 sont chacun un nombre entier compris entre 0 et 4.
PCT/JP2001/000292 2000-01-18 2001-01-18 Film polyester ininflammable WO2001053377A1 (fr)

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JP2000-9285 2000-01-18
JP2000009285 2000-01-18
JP2000269051 2000-09-05
JP2000-269051 2000-09-05
JP2000356262 2000-11-22
JP2000-356263 2000-11-22
JP2000-356262 2000-11-22
JP2000356263 2000-11-22

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WO2001053377A1 true WO2001053377A1 (fr) 2001-07-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013857A (ja) * 2006-07-03 2008-01-24 Aqua House Kk フィルム状接着芯地
JP2009126970A (ja) * 2007-11-26 2009-06-11 Teijin Dupont Films Japan Ltd ポリエステルフィルム
JP2014046652A (ja) * 2012-09-04 2014-03-17 Mitsubishi Plastics Inc 難燃性を有する黒色ポリエステルフィルム
JP2016079231A (ja) * 2014-10-11 2016-05-16 三菱樹脂株式会社 白色難燃性ポリエステルフィルム
JP2020517786A (ja) * 2017-04-25 2020-06-18 ポリテクニール，エスアエス 難燃性ポリマー、その製造方法及びそれを含有する熱可塑性ポリマー組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5596457B2 (ja) * 2010-07-29 2014-09-24 三菱樹脂株式会社 難燃性ポリエステル系樹脂組成物及びこれを用いてなる成形品

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08217961A (ja) * 1995-02-15 1996-08-27 Toray Ind Inc ポリエステル組成物およびそれからなる成形品
JP2000109549A (ja) * 1998-10-06 2000-04-18 Mitsubishi Rayon Co Ltd 難燃性ポリエステル樹脂およびその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08217961A (ja) * 1995-02-15 1996-08-27 Toray Ind Inc ポリエステル組成物およびそれからなる成形品
JP2000109549A (ja) * 1998-10-06 2000-04-18 Mitsubishi Rayon Co Ltd 難燃性ポリエステル樹脂およびその製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013857A (ja) * 2006-07-03 2008-01-24 Aqua House Kk フィルム状接着芯地
JP2009126970A (ja) * 2007-11-26 2009-06-11 Teijin Dupont Films Japan Ltd ポリエステルフィルム
JP2014046652A (ja) * 2012-09-04 2014-03-17 Mitsubishi Plastics Inc 難燃性を有する黒色ポリエステルフィルム
JP2016079231A (ja) * 2014-10-11 2016-05-16 三菱樹脂株式会社 白色難燃性ポリエステルフィルム
JP2020517786A (ja) * 2017-04-25 2020-06-18 ポリテクニール，エスアエス 難燃性ポリマー、その製造方法及びそれを含有する熱可塑性ポリマー組成物

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